Hair coloring compositions

ABSTRACT

A hair coloring composition comprising: (a) from about 0.0003 moles (per 100 g of composition) to less than about 0.09 moles (per 100 g of composition) of an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent; wherein the pH of each of (a) and (b) is in the range of from about 1 to about 6 and wherein the combined mixture of (a) and (b) has a pH in the range of from about 1 to about 6. The products can provide excellent hair coloring and in-use efficacy benefits including excellent initial color and good wash fastness in combination with reduced hair damage at low pH.

TECHNICAL FIELD

[0001] This invention relates to hair coloring compositions andprocesses for coloring hair, and more especially to hair coloringcompositions comprising an inorganic peroxygen oxidising agent incombination with an oxidative hair coloring agent at an acidic pH ofbetween about 1 and about 6.

BACKGROUND OF THE INVENTION

[0002] The desire to alter the color of human hair is not a facet ofmodern times. Since the days of the Roman Empire the color of human hairhas been routinely altered to accommodate the changes of fashion andstyle. However the attainment of precise initial colors which areretained by the hair for a desirable period has remained a more elusivegoal. The difficulties in the development of hair coloring compositionswhich can deliver precise long-lasting colors are in part due to theinherent structure of the hair itself and in part due to the necessaryconditions of effective hair coloration processes.

[0003] In general, the condition and structure of human hair is notregular along the length of the hair shaft. Human hair is subject tovarious chemical and mechanical treatments such as combing, brushing,shampooing, heating, perming as well as exposure to the sun. As such,the hair at the ends of the hair shaft will generally exhibit greatersigns of damage relative to the new growth close to the scalp. Thisdamage can lead to inconsistent coloration when the hair is dyed due toirregular uptake of the hair coloring agents along the length of thehair shaft.

[0004] Once the hair has been colored there is a desire for the color tobe resistant to fading, as occasioned by the actions of washing (alsoknown as wash fastness), perspiration, hair spray and other exteriorfactors such as the action of the sun, and further that the color beretained in a consistent manner for a predictable period of time.Additionally damage to the hair that can lead to irregular dye uptake asdiscussed above, can lead to increased fading of the damaged portions ofthe hair and consequently, irregular levels of color fade over time. Anadditional difficulty commonly associated with the dyeing of human hairis the need for dye systems which avoid any adverse effect on the hairand skin of the user, such as brittle hair, or, irritation of the skin,or, staining (coloring) of the skin.

[0005] Thus, it would be desirable to develop a hair coloringcomposition which exhibits reduced fade, provides improved resistance towash out during a regular cleansing regimen, can deliver substantiallyconsistent hair color results throughout the hair, which has reducedirritant effect on the skin, which has reduced staining on the skin,which has reduced adverse effects on the hair of the user and also todevelop a convenient and easy-to-use method for the delivery of such ahair coloring composition to the hair.

[0006] Over the years significant effort has been directed towards theelimination of many of the problems associated with the dyeing of humanhair. Various approaches to hair dyeing have been developed, theseinclude, direct action dyes, natural dyes, metallic dyes and oxidativedyes.

[0007] To color human or animal hair using oxidative dye technology thehair is generally treated with a mixture of oxidative hair coloringagents and an oxidising agent. Hydrogen peroxide is the most commonlyused oxidising agent. However, in addition to oxidising the oxidativecoloring agents, hydrogen peroxide treatment of the hair can alsosolubilise and decolorise the colored melanin component in the hairwhich can lead to undesirable hair qualities, such as brittleness andhair damage. This is in part due to the conditions of conventionalperoxide treatment, as part of the hair coloring process, when conductedat high pH (>pH 9), extended exposure (from 10 to 60 minutes) and arelatively high concentration of oxidising solution (between about 20%to about 40% volume of oxygen i.e. about 6 -12% wt.) in order to delivereffective dye oxidisation.

[0008] Oxidative hair coloring agents and peroxygen oxidising agents canbe used to deliver a variety of hair colors to the hair. Howeversubstantial improvement is needed in the areas of color saturation,color development, precise initial color consistency, improved washfastness, improved hair condition and levels of hair damage.

[0009] Thus there is a need for oxidative hair coloring compositionswhich effectively dye the hair but avoid or reduce damage to the hair,which can color the hair effectively and avoid or reduce irritationand/or staining to the skin of the user.

[0010] Typically, hair coloring compositions containing oxidative haircoloring agents are formulated at high pH (from about pH 9 to about pH12) and commonly contain, in addition to the oxidative hair coloringagents and an inorganic peroxygen oxidising agent, peroxide activatingagents and a variety of additional cosmetic, coloring agent andperoxygen oxidising agent stabilising agents. It is also known thatenhanced oxidative hair coloring agent oxidation can be achieved via theuse of a hair swelling agent (HSA). Such HSA's enhance the oxidising andcoloring process by swelling the hair fibres to aid both the diffusionof the peroxygen oxidising agent and the oxidative hair coloring agentsinto the hair and enabling faster, more thorough dye oxidisation andhair coloring. A common HSA is an aqueous (alkaline) solution containinga source of ammonia, such as ammonium hydroxide. However ammonia cancause skin irritation and in addition has an undesirable odour and cancause lacrimatory effects.

[0011] Thus, it would be desirable to develop a hair coloringcomposition having desirable odour characteristics comprising oxidativehair coloring agents which delivers improved hair coloring benefitsand/or delivers faster hair coloring without the need for an HSA.

[0012] It has now been found that the combination of inorganic peroxygenoxidising agents with one or more oxidative hair coloring agents at a pHbelow the internal pH of hair, between about pH 1 to about pH 6, andoptionally, certain, additional oxidising agents, in hair coloringcompositions can deliver excellent initial hair color in combinationwith improved color and wash fastness of the hair color over time,desirable color saturation and vividness attributes, reduced hairdamage, reduced skin irritation, reduced skin staining and moreefficient dyeing. Furthermore, it has been found that the efficiency ofcolor development (color change) from the inorganic peroxygen oxidisingagents and particular oxidative hair coloring agents of the presentinvention is improved under the low pH conditions according to thepresent invention. In addition, it has been found that the hair coloringcompositions according to the present invention can deliver theseexcellent hair coloring attributes results with minimal hair damage, atlow pH (about 1 to about 6 ).

[0013] It is an object of the present invention to provide low pH haircoloring compositions which deliver the combination of improved haircoloring attributes, such as, longer lasting color (reduced fade),initial color generation, increased color uptake and color consistencyacross hair types. Hair types as defined herein means hair of varyingage and condition i.e. virgin untreated, grey, permed, bleached etc.

[0014] It is an additional object of the present invention to providelow pH hair coloring compositions which have reduced levels of skinirritation and/or skin staining versus conventional high pH systems andwhich impart minimal damage to the hair fibres and reduced staining ofskin in combination with an acceptable odor.

[0015] It is a still further object of the present invention to providelow pH hair coloring compositions which exhibit increased efficacy(improved color development). Color development as defined herein,means, the change in the hair color, expressed in terms of Delta E, asdefined in the Experimental section herein after). It is a yet furtherobject of the present invention to provide coloring compositions withreduced damage to the skin and/or hair which can deliver equivalentcolor development (versus conventional high pH systems) in combinationwith improved washfastness and color consistency while using less dyeand/or less of the oxidising agent.

[0016] It has been found that the above objects can be met by the low pHhair coloring compositions according to the present invention.

[0017] In addition, conventional, high pH, hair coloring compositionstypically comprise at least two separately packaged components, whichare generally, oxidising agent (at low pH) and oxidative hair coloringagents (at high pH). These separately packaged components are admixed athigh pH just prior to application to the hair. Such an admixing step canbe messy and inconvenient to the user. Typically, conventional coloringcompositions, comprising oxidising agent and oxidative hair coloringagent, need to be used soon after admixing due to degradation of theresulting coloring composition. As such, excess admixed coloringcomposition is disposed of after application of the required amount tothe hair. It has been found that the oxidant(s) and dyes of the presentinvention can be admixed in a singly packaged low pH mixture withimproved stability versus conventional, high pH, oxidative dye systems.The singly packaged low pH coloring compositions of the presentinvention are suitable for use in a multi-application format (i.e. theconsumer can use a single package for several color applications over aperiod of time). It has also been found that, at low pH, both theoxidising agent and oxidative hair coloring agents are stable over time,and can be stored as such.

[0018] Thus it is another object of the present invention to providesingly packaged hair coloring compositions which are fast acting, simpleto use and re-usable.

[0019] It is a further object of the present invention to provide haircoloring compositions comprising stable, separately packaged oxidant(s)and oxidative hair coloring agent(s) which remain stable at low pH bothwhen stored individually or when mixed.

[0020] All percentages are by weight of the final compositions in theform intended to be used unless specified otherwise.

SUMMARY OF THE INVENTION

[0021] The subject of the present invention is a hair coloringcomposition suitable for the treatment of human or animal hair.

[0022] According to one aspect of the present invention, there isprovided a hair coloring composition comprising:

[0023] (a) from about 0.0003 moles (per 100 g of composition) to lessthan about 0.09 moles (per 100 g of composition) of an inorganicperoxygen oxidising agent; and

[0024] (b) an oxidative hair coloring agent;

[0025] wherein the pH of each of (a) and (b) is in the range of fromabout 1 to about 6 and wherein the combined mixture of (a) and (b) has apH in the range of from about 1 to about 6 .

[0026] It is to be understood that the percentage weights of thecomposition components herein are expressed in terms of the totalcomposition, and includes the composition in the form of intended use

[0027] According to a further aspect of the present invention, there isprovided:

[0028] A method for coloring hair wherein a hair coloring mixture ispresent in a single package and applied directly to the hair and whereinthe hair coloring mixture comprises:

[0029] (a) from about 0.0003 moles (per 100 g of composition) to lessthan about 0.09 moles (per 100 g of composition) of an inorganicperoxygen oxidising agent; and

[0030] (b) an oxidative hair coloring agent;

[0031] wherein the pH of each of (a) and (b), is in the range of fromabout 1 to about 6 and wherein the combined mixture of (a) and (b), hasa pH in the range of from about 1 to about 6.

[0032] According to a still further aspect of the present invention,there is provided:

[0033] A method for coloring hair wherein a hair coloring composition ispresent as separately packaged components (a) and (b) and wherein thehair coloring composition comprises:

[0034] (a) from about 0.0003 moles (per 100 g of composition) to lessthan about 0.09 moles (per 100 g of composition) of an inorganicperoxygen oxidising agent wherein the pH of (a), is in the range of fromabout 1 to about 6; and

[0035] (b) an oxidative hair coloring agent wherein the pH of (b), is inthe range of from about 1 to about 6;

[0036] wherein each of (a) and (b) are stable at pHs in the range offrom about 1 to about 6 and wherein the combined mixture of (a) and (b)is stable over time and has a pH in the range of from about 1 to about6.

[0037] According to an additional object of the present invention thereis provided a hair coloring composition comprising:

[0038] (a) an inorganic peroxygen oxidising agent; and

[0039] (b) an oxidative hair coloring agent;

[0040] wherein the pH of each of (a) and (b) is in the range of fromabout 1 to about 6, wherein the combined mixture of (a) and (b) has a pHin the range of from about 1 to about 6, wherein (a) and (b) are in theform of intended use, and wherein the molar level of (a) is from aboutfrom about 0.0003 moles (per 1 g of composition) to less than about 0.09moles (per 100 g of composition).

DETAILED DESCRIPTION OF THE INVENTION

[0041] As used herein the term ‘hair’ to be treated may be ‘living’ i.e.on a living body or may be ‘non-living’ i.e. in a wig, hairpiece orother aggregation of non-living fibres, such as though used in textilesand fabrics. Mammalian, preferably human hair is preferred. Howeverwool, fur and other melanin containing fibres are suitable substratesfor the compositions according to the present invention.

[0042] As used herein the term ‘hair coloring composition’ is used inthe broad sense in that it is intended to encompass compositionscontaining the combinations herein of a low pH (from about 1 to about 6) mixture of inorganic peroxygen based dye oxidising agent and anoxidative coloring agent. Moreover, it is also intended to includecomplex compositions which contain other components which may or may notbe active ingredients. Thus, the term ‘hair coloring composition’ isintended to apply to compositions which contain, in addition to amixture of active oxidising agents and oxidative coloring agents, suchthings as, by way of example, oxidising aids, sequestrants, stabilisers,thickeners, buffers, carriers, surfactants, solvents, antioxidants,polymers, non-oxidative dyes and conditioners.

[0043] As discussed above, the hair coloring compositions according tothe present invention comprise from about 0.0003 moles (per 100 g ofcomposition) to less than about 0.09 moles (per 100 g of composition) ofan inorganic peroxygen based oxidising agent (a), in combination with anoxidative hair coloring agent (b) wherein the pH of each of (a) and (b)is in the range of from about 1 to about 6 and wherein the pH of thecombined mixture of (a) and (b) is in the range of from about 1 to about6. Preferably, the pH of either (a) and/or (b) is in the range of fromabout 1.5 to about 5.8, more preferably from about 1.8 to about 5.5,most preferably from about 2 to about 5 and especially from about 3.5 toabout 4.5 and wherein the preferred pH of the combined mixture of (a)and (b) is in the range of from about 1.5 to about 5.8, more preferablyfrom about 1.8 to about 5.5, most preferably from about 2 to about 5 andespecially from about 3.5 to about 4.5. In addition to the inorganicperoxygen oxidising agent, the compositions may optionally comprise(among other ingredients) a preformed organic peroxyacid oxidisingagent. Organic peroxyacid as used herein is intended to cover anyorganic peroxy acid material which can act either alone or incombination with a peroxygen oxidising agent to oxidise dye precursors.

The Dye Oxidisation and Hair Coloring Processes

[0044] It is understood by those familiar in the art that tosuccessfully color human or animal hair with oxidative dyes it isgenerally necessary to treat the hair with a mixture of oxidising agentand oxidative hair coloring agent. As herein before discussed the mostcommon oxidising agent is hydrogen peroxide.

[0045] Hydrogen peroxide has a pKa in the range of from about 11.2 toabout 11.6, and, as such is generally used as a dye oxidising agent atpHs in the range of from about 9 to about 12. Surprisingly, it has nowbeen found that improved color development is observed in combinationwith improved color washfastness, in the low pH oxidative systemsaccording to the present invention, at pHs in the range of from about pH1 to about pH 6, preferably from about pH 1.5 to about pH 5.8, morepreferably from pH 1.8 to about pH 5.5, most preferably from about pH 2to about pH 5, and especially from about pH 3.5 to about pH 4.5.

Inorganic Oxidizing Agents

[0046] The compositions of the invention comprise as an essentialfeature at least one inorganic oxidising agent (hereinafter called‘inorganic peroxygen oxidising agent’). The inorganic peroxygenoxidising agent should be safe and effective for use in the compositionsherein. Preferably, the inorganic peroxygen oxidising agents suitablefor use herein will be soluble in the compositions according to thepresent invention when in liquid form or in the form intended to beused. Preferably, inorganic peroxygen oxidising agents suitable for useherein will be water-soluble. Water soluble oxidising agents as definedherein means agents which have a solubility to the extent of about 10 gin 1000 ml of deionised water at 25° C. (“Chemistry” C. E. Mortimer. 5thEdn. p277).

[0047] The inorganic peroxygen oxidising agents useful herein aregenerally inorganic peroxygen materials capable of yielding peroxide inan aqueous solution. Inorganic peroxygen oxidising agents are well knownin the art and include hydrogen peroxide, inorganic alkali metalperoxides such as sodium periodate, sodium perbromate and sodiumperoxide, and inorganic perhydrate salt oxidising compounds, such as thealkali metal salts of perborates, percarbonates, perphosphates,persilicates, persulphates and the like. These inorganic perhydratesalts may be incorporated as monohydrates, tetrahydrates etc. Mixturesof two or more of such inorganic peroxygen oxidising agents can be usedif desired. While alkali metal bromates and iodates are suitable for useherein the bromates are preferred. Highly preferred for use in thecompositions according to the present invention is hydrogen peroxide.

[0048] It has been found that, under the low pH conditions according tothe present invention, it is possible to deliver both improved initialcolor development, color consistency, washfastness and color intensityversus conventional, high pH, systems (using equivalent levels ofperoxide and dyes) and also equivalent color development (detailedhereinafter in the Experimental Data section in terms of Delta E) versusconventional systems at high pH, while using substantially less of theinorganic peroxygen oxidising agent (up to 75% less) as well asdelivering equivalent color development versus conventional, high pH,systems while using substantially less oxidative hair coloring agent (upto 50% less). Thus, the low pH hair coloring compositions according tothe present invention can be formulated to reduce the level of damage tothe hair and levels of skin irritation and staining. Furthermore, as thelow pH hair coloring compositions according to the present invention canbe formulated without ammonia there are no ammonia related odor or skinirritation negatives associated with these compositions.

[0049] The inorganic peroxygen oxidising agent is present in thecompositions according to the present invention at a molar level of fromabout 0.000294 moles (per 100 g of composition) to less than about0.0882 moles (per 100 g of composition), preferably, the inorganicperoxygen oxidising agent is present at a molar level of from about0.0003 moles to about 0.08 moles, more preferably from about 0.0003moles to about 0.06 moles, even more preferably from about 0.0003 molesto about 0.04 moles, most preferably from about 0.0003 mole to about0.03 moles, especially from about 0.0003 moles to about 0.02 moles andmost especially from about 0.0003 moles to about 0.015 moles (per 100 gof composition).

[0050] In preferred compositions according to the present invention theinorganic peroxygen oxidising agent is present at a level of from about0.01% to less than about 3%, preferably from about 0.01% to about 2.5%,more preferably from about 0.01% to about 2%, even more preferably fromabout 0.01% to about 1%, most preferably from about 0.01% to about 0.8%,especially from about 0.01% to about 0.55% and especially from about0.01% to about 0.5% by weight of composition.

Preformed Organic Peroxyacid

[0051] The compositions according to the present invention may,optionally, contain, in addition to the inorganic peroxygen oxidisingagent(s), one or more preformed organic peroxyacid oxidising agents.

[0052] Suitable, additional, optional, organic peroxyacid oxidisingagents for use in the coloring compositions according to the presentinvention have the general formula:

R—C(O)OOH

[0053] wherein R is selected from saturated or unsaturated, substitutedor unsubstituted, straight or branched chain, alkyl, aryl or alkarylgroups with from 1 to 14 carbon atoms.

[0054] A class of organic peroxyacid compounds suitable for use hereinare the amide substituted compounds of the following general formulae:

R¹—C—N—R²—C—OOH R^(1—N—C—R) ²—C—OOH O R⁵O or R⁵O O

[0055] wherein R¹ is, a saturated or unsaturated alkyl or alkaryl group,or an aryl group, having from 1 to 14 carbon atoms, R² is, a saturatedor unsaturated alkyl or alkaryl group, or an aryl group, having from 1to 14 carbon atoms, and R⁵ is H or, a saturated or unsaturated alkyl oralkaryl group, or an aryl group, having from 1 to 10 carbon atoms. Amidesubstituted organic peroxyacid compounds of this type are described inEP-A-0,170,386.

[0056] Other suitable organic peroxyacid oxidising agents includeperacetic, pernanoic, nonylamidoperoxycaproic acid (NAPCA), perbenzoic,m-chloroperbenzoic, di-peroxy-isophthalic, mono-peroxyphthalic,peroxylauric, hexanesulphonyl peroxy propionic, N,N-phthaloylaminoperoxycaproic, monoper succinic, nonanoyloxybenzoic,dodecanedioylmonoperoxybenzoic, nonylamide of peroxyadipic acid, diacyland tetraacylperoxides, especially diperoxydodecanedioic acid,diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid andderivatives thereof. Mono- and diperazelaic acid, mono- anddiperbrassylic acid and N-phthaloylaminoperoxicaproic acid andderivatives thereof are also suitable for use herein.

[0057] The preformed organic peroxyacid oxidising agents should be safeand effective for use in the compositions herein. Preferably, thepreformed organic peroxyacid oxidising agents suitable for use hereinwill be soluble in the compositions according to the present inventionwhen in liquid form and in the form intended to be used. Preferably,organic peroxyacid oxidising agents suitable for use herein will bewater-soluble. Water-soluble preformed organic peroxyacid oxidisingagents as defined herein means agents which have a solubility to theextent of about 10 g in 1000 ml of deionised water at 25° C.(“Chemistry” C. E. Mortimer. 5th Edn. p277).

[0058] The preferred peroxyacid materials suitable for use herein areselected from peracetic and pernanoic acids and mixtures thereof.

[0059] The preformed organic peroxyacid oxidising agent, where present,is present at a molar level of from about 0.0001 moles to about 0.1moles (per 100 g of composition), more preferably from about 0.001 molesto about 0.05 moles, most preferably from about 0.003 moles to about0.04 moles and especially from about 0.004 moles to about 0.03 moles per100 g of the hair coloring composition.

[0060] The preformed organic peroxyacid oxidising agent, where present,is preferably present at a level of from about 0.01% to about 8%, morepreferably from about 0.1% to about 6%, most preferably from about 0.2%to about 4%, and especially from about 0.3% to about 3% by weight of thehair coloring composition. The weight ratio of the inorganic peroxygenoxidising agent to the preformed organic peroxy acid is preferably inthe range of from about 0.0125:1 to about 500:1, more preferably fromabout 0.0125:1 to about 50:1.

[0061] In addition to the inorganic peroxygen oxidising agents and theadditional, optional, preformed organic peroxyacid oxidising agentssuitable for use herein, the compositions according to the presentinvention may optionally comprise additional organic peroxides such asurea peroxide, melamine peroxide and mixtures thereof. The level oforganic peroxide, where present, is from about 0.01% to about 3%,preferably from about 0.01% to about 2%, more preferably from about 0.1%to about 1.5% and most preferably from about 0.2% to about 1% by weightof composition.

Hair Coloring Agents

[0062] The low pH hair coloring compositions of the present inventioninclude as an essential feature an oxidative hair coloring agent. Suchoxidative hair coloring agents are used in combination with the peroxidebased oxidising systems of the present invention to formulate permanent,demi-permanent, semi-permanent or temporary hair dye compositions at lowpH.

[0063] Permanent hair dye compositions as defined herein arecompositions which once applied to the hair are substantially resistantto wash-out. Demi-permanent hair dye compositions as defined herein arecompositions which are substantially removed from the hair after up to24 washes. Semi-permanent hair dye compositions as defined herein arecompositions which once applied to the hair are substantially removedfrom the hair after up to 10 washes. Temporary hair dye compositions asdefined herein are compositions which once applied to the hair aresubstantially removed from the hair after up to 2 washes. Thesedifferent types of hair coloring compositions can be formulated via thespecific combination of oxidant and/or dyes at different levels andratios. Wash out as defined herein is the process by which hair color isremoved from the hair over time during normal hair cleansing regimen.Washfastness as defined herein, means, the resistance of the dyed hairto wash out. Washfastness, as defined herein, can be measured in termsof the relative color change in the dyed hair (Delta E) over severalwashes (shampoos). Substantial removal of dye from the hair as definedherein means the color change in the dyed hair (Delta E) is greater thanabout 2 after up to 10 washes.

[0064] The concentration of each oxidative hair coloring agent in thelow pH coloring compositions according to the present invention is fromabout 0.001% to about 3% by weight and is preferably from about 0.01% toabout 2% by weight.

[0065] The total combined level of oxidative hair coloring agents in thecompositions according to the present invention is from about 0.001% toabout 5%, preferably from about 0.01 % to about 4%, more preferably fromabout 0.1% to about 3%, most preferably from about 0.1% to about 1% byweight.

[0066] Typically, in conventional hair coloring compositions the totallevel of oxidative hair coloring agents present in the composition is inthe range of from about 0.2% to about 3.5% by weight. Accordingly, thecompositions according to the present invention can display improvedhair coloring attributes, such as initial color development and initialcolor consistency in combination with improved washfastness over time,when compared to conventional, high pH, systems having similar levels ofdye. Color consistency, as used herein, means, both the relativepredictability of the initial color development and improved colorretention over time across different hair types.

[0067] The efficacy of the oxidative dyes is improved at low pH suchthat the compositions of the present invention are valuable for thedelivery of good high intensity colors (dark colors) with reduced levelsof dye. In particular, good hair coloring results in combination withequivalent color development (versus high pH systems) can be achievedusing the inorganic peroxygen oxidising agents of the present inventionand substantially less dye versus conventional, high pH, hair coloringcompositions.

[0068] Thus according to a further aspect of the present invention thereis provided a hair coloring composition comprising:

[0069] (a) from about 0.0003 moles (per 100 g of composition) to lessthan about 0.09 moles (per 100 g of composition) of an inorganicperoxygen oxidising agent; and

[0070] (b) an oxidative hair coloring agent; and

[0071] (c) a diluent suitable for application to the hair;

[0072] wherein the pH of each of (a) and (b) is in the range of fromabout 1 to about 6 and wherein the pH of the composition is in the rangeof from about 1 to about 6 .

[0073] As herein before described, it has also been found that thecombination of inorganic peroxygen oxidising agents with oxidative haircoloring agent at low pH is valuable for the delivery of excellent haircoloring attributes in combination with reduced levels of hair damage,skin irritation and skin staining in combination with an improved odorprofile (versus conventional high pH compositions). A further benefit ofthe low pH coloring compositions according to the present invention isthat reduced levels of skin staining can be observed from suchcompositions, versus conventional, high pH, compositions.

[0074] Thus according to a still further aspect of the present inventionthere is provided a hair coloring composition capable of delivering alight auburn colour to light brown hair having 40% grey comprising:

[0075] (a) from about 0.0003 moles (per 100 g of composition) to lessthan about 0.09 moles (per 100 g of composition) of an inorganicperoxygen oxidising agent; and

[0076] (b) an oxidative hair coloring agent; and

[0077] (c) a diluent suitable for application to the hair;

[0078] wherein the pH of components (a) and (b) are each in the range offrom about 1 to about 6 and wherein the pH of the composition is in therange of from about 1 to about 6 and wherein the change in level of skinstaining after product application (Delta E) is less than about 4,preferably less than about 3, more preferably less than about 2.7. Lightbrown hair having 40% grey coverage is defined in terms of L, a, bvalues as having an ‘L’ value in the range of from about 35 to about 37,an ‘a’ value in the range of from about 4.5 to about 5.5 and a ‘b’ valuein the range of from about 11.5 to about 12.7.

[0079] Without being limited by any particular theory, it is believedthat, these improvements (in respect of reduced skin irritation and/ orstaining) result from the combination of (a) reduced levels of dyes andlow pH; (b) the reduction of paraphenylene diamine (PPD) contactsensitisation at low pH (high levels of PPD have been shown to displaycontact sensitisation at high pH, but not at low pH); (c) theelimination of the formation of nitrobenzene contact sensitisers (whichcan occur in high pH compositions); (d) reduced levels of skin stainingat low pH versus high pH, and; (e) the reduction in skin irritation andodor negatives as a result of the elimination of ammonia and the use ofalternative oxidising agents in the low pH dyeing compositions accordingto the present invention.

Oxidative Hair Coloring Processes

[0080] Any oxidative hair coloring agent can be used in the compositionsaccording to the present invention. Typically, but without intending tobe limited thereby, oxidative hair coloring agents, consist essentiallyof at least two components, which are collectively referred to as dyeforming intermediates (or precursors). Dye forming intermediates canreact in the presence of a suitable oxidant to form a colored molecule.

[0081] The dye forming intermediates used in oxidative hair colorantsinclude: aromatic diamines, aminophenols, various heterocycles, phenols,napthols and their various derivatives. These dye forming intermediatescan be broadly classified as; primary intermediates and secondaryintermediates. Primary intermediates, which are also known as oxidativedye precursors, are chemical compounds which become activated uponoxidation and can then react with each other and/or with couplers toform colored dye complexes. The secondary intermediates, also known ascolor modifiers or couplers, are generally colorless molecules which canform colors in the presence of activated precursors/primaryintermediates, and are used with other intermediates to generatespecific color effects or to stabilise the color.

[0082] Primary intermediates suitable for use in the compositions andprocesses herein include: aromatic diamines, polyhydric phenols, aminophenols and derivatives of these aromatic compounds (e.g., N-substitutedderivatives of the amines, and ethers of the phenols). Such primaryintermediates are generally colorless molecules prior to oxidation.

[0083] While not wishing to be bound by any particular theory it isproposed herein that the process by which color is generated from theseprimary intermediates and secondary coupler compounds generally includesa stepwise sequence whereby the primary intermediate can becomeactivated (by oxidation), and then enjoins with a coupler to give adimeric, conjugated colored species, which in turn can enjoin withanother ‘activated’ primary intermediate to produce a trimericconjugated colored molecule.

Chemistry of Oxidative Hair Coloration Across pH

[0084] While not wishing to be bound by any particular theory, it isgenerally understood that conventional oxidative dyeing typically occursbetween oxidative precursor molecules, oxidative coupler molecules and aperoxygen oxidising agent at high pH (8 -10). Typical precursors include1,4-disubstituted benzene derivatives and typical couplers include 1,2-or 1,3-disubstituted benzene derivatives.

[0085] It is generally accepted that the pH within the hair shaft, ofhuman hair, is around pH 5.5 to pH 6 (C. R. Robbins, Chemical andPhysical Behaviour of Human Hair, 2nd Ed. p157), and that the hair hasan inherent buffering capacity in this pH range.

[0086] Surpisingly it has now been found that, oxidative hair colorationat pH 6 or less with oxidising agents, at a molar level of from about0.000294 moles (per 100 g of composition) to less than about 0.0883moles 9per 100 g of composition), and an oxidative hair coloring agent,is valuable for the delivery of excellent initial hair color incombination with improved color and wash fastness of the hair color overtime, desirable color saturation and vividness attributes, reduced hairdamage, reduced skin irritation, reduced skin staining and moreefficient dyeing. Furthermore, it has been found that the efficiency ofcolor development (i.e., increased color change) from the inorganicperoxygen oxidising agents and the oxidative hair coloring agents of thepresent invention is improved under the low pH conditions according tothe present invention. In addition, it has been found that the low pHhair coloring compositions according to the present invention candeliver these excellent hair coloring attributes results with minimalhair damage.

[0087] It has also been found that at pH levels of less than pH 6,preferably from abour pH 1.5 to 5.8, more preferably from pH 1.8 to 5.5,and most preferably from about pH 2 to pH 5 and especially from about pH3.5 to about pH 4.5 further improvements in color development areacheived.

Oxidative Dye Precursors

[0088] In general terms, oxidative dye primary intermediates includethose monomeric materials which, on oxidation, form oligomers orpolymers having extended conjugated systems of electrons in theirmolecular structure. Because of the new electronic structure, theresultant oligomers and polymers exhibit a shift in their electronicspectra to the visible range and appear colored. For example, oxidativeprimary intermediates capable of forming colored polymers includematerials such as aniline, which has a single functional group andwhich, on oxidation, forms a series of conjugated imines and quinoiddimers, trimers, etc. ranging in color from green to black. Compoundssuch as p-phenylenediamine, which has two functional groups, are capableof oxidative polymerization to yield higher molecular weight coloredmaterials having extended conjugated electron systems. Oxidative dyesknown in the art can be used in the low pH compositions according to thepresent invention. A representative list of primary intermediates andsecondary couplers suitable for use herein is found in Sagarin,“Cosmetic Science and Technology”,” Interscience, Special Ed. Vol. 2pages 308 to 310. It is to be understood that the primary intermediatesdetailed below are only by way of example and are not intended to limitthe compositions and processes herein.

[0089] The typical aromatic diamines, polyhydric phenols, amino phenols,and derivatives thereof, described above as primary intermediates canalso have additional substituents on the aromatic ring, e.g. halogen,aldehyde, carboxylic acid, nitro, sulfonic acid and substituted andunsubstituted hydrocarbon groups, as well as additional substituents onthe amino nitrogen and on the phenolic oxygen, e.g. substituted andunsubstituted alkyl and aryl groups.

[0090] Examples of suitable aromatic diamines, amino phenols, polyhydricphenols and derivatives thereof, respectively, are compounds having thegeneral formulas (I), (II) and (III) below:

[0091] OR

[0092] wherein Y is hydrogen, halogen, (e.g. fluorine, chlorine, bromineor iodine), nitro, amino, hydroxyl,

[0093] —COOM or —SO₃M (where M is hydrogen or an alkali or alkalineearth metal, ammonium, or substituted ammonium wherein one or morehydrogens on the ammonium ion is replaced with a 1 to 3 carbon atomalkyl or hydroxyalkyl radical), wherein R₁, R₂, R₃ and R₄ are the sameor different from each other and are selected from the group consistingof hydrogen, C₁ to C₄ alkyl or alkenyl and C₆ to C₉ aryl, alkaryl oraralkyl, and R₅ is hydrogen, C₁ to C₄ unsubstituted or substituted alkylor alkenyl wherein the substituents are selected from those designatedas Y, above, or C₆ to C₉ unsubstituted or substituted aryl, alkaryl oraralkyl wherein the substituents are selected from those defined as Y,above. Since the precursors of formula (I) are amines, they can be usedherein in the form of peroxide-compatible salts, as noted, wherein Xrepresents peroxide-compatible anions of the type herein beforedetailed. The general formula of the salt indicated is to be understoodto encompass those salts having mono-, di-, and tri-negative anions.

[0094] Specific examples of formula (I) compounds are:o-phenylenediamine, m-phenylenediamine, p-phenylenediamine,2-chloro-p-phenylenediamine, 2-iodo-p-phenylenediamine,4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine,1,3,5-triaminobenzene, 2-hydroxy-p-phenylenediamine, 2,4-diaminobenzoicacid, sodium 2,4-diaminobenzoate, calcium di-2,4-diaminobenzoate,ammonium 2,4-diaminobenzoate, trimethylammonium 2,4-, diaminobenzoate,tri-(2-hydroxyethyl)ammonium 2,4-diaminobenzoate,2,4-diaminobenzaldehyde carbonate, 2,4-diaminobenzensulfonic acid,potassium 2,4-diaminobenzenesulfonate, N,N-diisopropyl-p-,phenylenediamine bicarbonate, N,N-dimethyl-p-phenylenediamine,N-ethyl-N′-(2-propenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine,N-phenyl-N-benzyl-p-phenylenediamine,N-ethyl-N′-(3-ethylphenyl)-p-phenylenediamine, 2,4-toluenediamine,2-ethyl-p-phenylenediamine, 2-(2-bromoethyl)-p-phenylenediamine,2-phenyl-p-phenylenediamine laurate, 4-(2,5-diaminophenyl)benzaldehyde,2-benzyl-p-phenylenediamine acetate,2-(4-nitrobenzyl)-p-phenylenediamine,2-(4-methylphenyl)-p-phenylenediamine,2-(2,5-diaminophenyl)-5-methylbenzoic acid, methoxyparaphenylenediamine,dimethyl-p-phenylenediamine, 2,5-dimethylpara-phenylenediamine,2-methyl-5-methoxy-para-phenylenediamine,2,6-methyl-5-methoxy-para-phenylenediamine,3-methyl-4-amino-N,N-diethylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,3-methyl-4-amino-N,N-bis(β-hydroxyethyl)aniline,3-chloro-4-amino-N,N-bis(β-hydroxyethyl)aniline,4-amino-N-ethyl-N-(carbamethyl)aniline,3-methyl-4-amino-N-ethyl-N-(carbamethyl )aniline,4-amino-N-ethyl-(β-piperidonoethyl)aniline,3-methyl-4-amino-N-ethyl-(β-piperidonoethyl)aniline,4-amino-N-ethyl-N-(β-morpholinoethyl)aniline,3-methyl-4-amino-N-ethyl-N-(β-morpholinoethyl)aniline,4-amino-N-ethyl-N-(β-acetylaminoethyl)aniline,4-amino-N-(β-methoxyethyl) aniline,3-methyl-4-amino-N-ethyl-N-(β-acetylaminoethyl) aniline,4-amino-N-ethyl-N-(β-mesylaminoethyl) aniline,3-methyl-4-amino-N-ethyl-N-(β-mesylaminoethyl) aniline,4-amino-N-ethyl-N-(β-sulphoethyl) aniline,3-methyl-4-amino-N-ethyl-N-(β-sulphoethyl) aniline,N-(4-aminophenyl)morpholine, N-(4-aminophenyl)piperidine,2,3-dimethyl-p-phenylenediamine, isopropyl-p-phenylenediamine,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine sulphate.

[0095] In highly preferred compositions according to the presentinvention the materials having general formulae (Ia) and (Ib) arepreferred.

[0096] except where R₁═R₂═Me, Et

[0097] and salt

[0098] except where R₁═R₂═Me

[0099] wherein Y is hydrogen, halogen, (e.g. fluorine, chlorine, bromineor iodine), nitro, amino, hydroxyl,

[0100] —COOM or —SO₃M (where M is hydrogen or an alkali or alkalineearth metal, ammonium, or substituted ammonium wherein one or morehydrogens on the ammonium ion is replaced with a 1 to 3 carbon atomalkyl or hydroxyalkyl radical), wherein RI, R₂, R₃ and R₄ are the sameor different from each other and are selected from the group consistingof hydrogen, C₁ to C₄ alkyl or alkenyl and C₆ to C₉ aryl, alkaryl oraralkyl, and R₅ is hydrogen, C ₁ to C₄ unsubstituted or substitutedalkyl or alkenyl wherein the substituents are selected from thosedesignated as Y, above, or C₆ to C₉ unsubstituted or substituted aryl,alkaryl or aralkyl wherein the substituents are selected from thosedefined as Y, above. Since the precursors of formula (I) are amines,they can be used herein in the form of peroxide-compatible salts, asnoted, wherein X represents peroxide-compatible anions of the typeherein before detailed. The general formula of the salt indicated is tobe understood to encompass those salts having mono-, di-, andtri-negative anions.

[0101] OR

[0102] where X and Y are the same as in formula (I), R₁ and R₂) can bethe same or different from each other and are the same as in formula(I), R₅ is the same as in formula (I) and R₆ is hydrogen or C₁ to C₄substituted or unsubstituted alkyl or alkenyl wherein the substituentsare selected from those defined as Y in formula (I).

[0103] Specific examples of formula (II) compounds are:

[0104] o-aminophenol, m-aminophenol, p-aminophenol,2-iodo-p-aminophenol, 2-nitro-p-aminophenol, 3 ,4-dihydroxyaniline,3,4-diaminophenol, chloroacetate, 2-hydroxy-4-aminobenzoic acid,2-hydroxy-4-aminobenzaldehyde, 3-amino-4-hydroxybenzenesulfonic acid,N,N-diisopropyl-p-aminophenol, N-methyl-N-(1-propenyl)-p-aminophenol,N-phenyl-N-benzyl-p-aminophenol sulphate,N-methyl-N-(3-ethylphenyl)-p-aminophenol, 2-nitro-5-ethyl-p-aminophenol,2-nitro-5-(2-bromoethyl)-p-aminophenol,(2-hydroxy-5-aminophenyl)acetaldehyde, 2-methyl-p-aminophenol,(2-hydroxy-5-aminophenyl)acetic acid,3-(2-hydroxy-5-aminophenyl)-1-propene,3-(2-hydroxy-5-aminophenyl)-2-chloro-1-propene, 2-phenyl-p-aminophenolpalmitate, 2-(4-nitrophenyl)-p-aminophenol, 2-benzyl-p-aminophenol,2-(4-chlorobenzyl-p-aminophenol perchlorate,2-(4-methylphenyl)-p-aminophenol,2-(2-amino-4-methylphenyl)-p-aminophenol, p-methoxyaniline,2-bromoethyl-4-aminophenyl ether phosphate, 2-nitroethyl-4-aminophenylether bromide, 2-aminoethyl-4-aminophenyl ether,2-hydroxyethyl-4-aminophenyl ether, (4-aminophenoxy)acetaldehyde,(4-aminophenoxy)acetic acid, (4-aminophenoxy)methanesulfonic acid,1-propenyl-4-aminophenyl ether isobutyrate, (2-chloro)-1-propenyl-4-aminophenyl ether, (2-nitro)-1-propenyl-4-aminophenyl ether,(2-amino)-propenyl-4-aminophenyl ether,(2-hydroxy)-1-propenyl-4-aminophenyl ether, N-methyl-p-aminophenol,3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol,2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol,2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol,2-hydroxymethyl-4-aminophenol, 3-hydroxymethyl-4-aminophenol.

[0105] According to the present invention compounds having the formulaIIa are not preferred:

[0106] wherein: R₁ is alkyl, hydroxy alkyl, carboxyalkyl or aminoalkyl;R₂ is hydrogen, alkyl or hydroxyalkyl groups; R₃ and R₅ are H or —ORwhere R is an alkyl or hydroxyalkyl substituents; R₄ is H, alkyl orNHR′; R₆ is H, alkyl, —OR or NHR′; R′ is H, alkyl, hydroxyalkyl: withthe proviso that a) only one of R₄ and R₆ are NHR′: b) R₃ and —OR₁ arenot both methoxy when when R₂, R₅ and R₆ are H and R₄ is NH₂; c) eitherR₃, or R₄, or R₅, or R₆ is H; d) R₃, R₄ and R₅ are not all H when R₆ isNH_(2,) R₂ is H and R₁ is methyl; e) if R1 is ethyl and R2, R3, R4 andR6 are H, R₄ is not NH₂; f) if R₁ is carboxyalkyl or aminoalkyl, R₄ isNHR′.

[0107] Specific examples of formula (III) compounds are:

[0108] o-hydroxyphenol (catechol), m-hydroxyphenol (resorcinol),p-hydroxyphenol (hydroquinone), 4-methoxyphenol, 2-methoxyphenol,4-(2-chloroethoxy) phenol, 4-(2-propenoxy) phenol,4-(3-chloro-2-propenoxy) phenol, 2-chloro-4-hydroxyphenol(2-chlorohydroquinone), 2-nitro-4-hydroxyphenol(2-nitrohydroquinone),2-amino-4-hydroxyphenol, 1,2,3-trihydroxybenzene (pyrogallol),2,4-dihydroxybenzaldehyde, 3,4-dihydoxybenzoic acid,2,4-dihydroxybenzenesulfonic acid, 3-ethyl-4-hydroxyphenol,3-(2-nitroethyl)-4-hydroxyphenol, 3-(2-propenyl)-4-hydroxyphenol,3-(3-chloro-2-propenyl)-4-hydroxyphenol, 2-phenyl-4-hydroxyphenol,2-(4-chlorophenyl)-4-hydroxyphenol, 2-benzyl-4-hydroxyphenol,2-(2-nitrophenyl)-4-hydroxyphenol, 2-(2-methylphenyl)-4-hydroxyphenol,2-(2-methyl-4-chlorophenyl)-4-hydroxyphenol,3-methoxy-4-hydroxy-benzaldehyde, 2-methoxy-4-( 1 -propenyl)phenol,4-hydroxy-3-methoxycinnamic acid, 2,5-dimethoxyaniline,2-methylresorcinol, alpha napthol and salts thereof.

[0109] In preferred compositions herein the following compound, havinggeneral formula (III) is not included:

[0110] Secondary coupling compounds (color modifiers), such as thosedetailed hereinafter, are preferably used in conjunction with theprimary intermediates herein and are thought to interpose themselves inthe colored polymers during their formation and to cause shifts in theelectronic spectra thereof, thereby resulting in slight color changes.

[0111] Secondary coupling compounds which are suitable for inclusion inthe coloring compositions and processes herein before described includecertain aromatic amines and phenols and derivatives thereof which do notproduce color singly, but which modify the color, shade or intensity ofthe colors developed by the primary oxidized dye intermediates. Certainaromatic amines and phenolic compounds, and derivatives thereof,including some aromatic diamines and polyhydric phenols of the typesdescribed by formulas (I), (Ia), (Ib), (II) and (III) above, but whichare well known in the art not to be suitable primary intermediates, aresuitable as couplers herein. Polyhydric alcohols are also suitable foruse as couplers herein.

[0112] The aromatic amines and phenols and derivatives described aboveas couplers can also have additional substituents on the aromatic ring,e.g., halogen, aldehyde, carboxylic acid, nitro, sulfonyl andsubstituted and unsubstituted by hydrocarbon groups, as well asadditional substituents on the amino nitrogen, or phenolic oxygen, e.g.substituted and unsubstituted alkyl and aryl groups. Again,peroxide-compatible salts thereof are suitable for use herein.

[0113] Examples of aromatic amines, phenols and derivatives thereof arecompounds of the general formulas (IV) and (V) below:

[0114] OR

[0115] wherein Z is hydrogen, C₁ and C₃ alkyl, halogen (e.g. fluorine,chlorine, bromine or iodine) nitro,

[0116] —COOM or SO₃M, (where M is hydrogen or an alkali or alkalineearth metal, ammonium or substituted ammonium wherein one or morehydrogens on the ammonium ion is replaced with a 1 to 3 carbon atomalkyl or hydroxyalkyl radical), wherein R₁ and R₂ are the same ordifferent and are selected from the group consisting of hydrogen, C₁ toC₄ alkyl or alkenyl and C₆ to C₉ aryl, alkaryl or aralkyl and R₇ ishydrogen, C₁ to C₄ unsubstituted or substituted alkyl or alkenyl whereinthe substituents are selected from those designated as Z above or C₆ toC₉ unsubstituted or substituted aryl, alkaryl or aralkyl wherein thesubstituents are selected from those defined as Z above and wherein X isas defined in formula (I).

[0117] Specific examples of formula (IV) compounds are:

[0118] aniline, p-chloroaniline, p-fluoroaniline, p-nitroaniline,p-aminobenzaldehyde, p-aminobenzoic acid, sodium-p-aminobenzoate,lithium-p-aminobenzoate, calcium di-p-aminobenzoate,ammonium-p-aminobenzoate, trimethylammonium-p-aminobenzoate,tri(2-hydroxyethyl)-p-aminobenzoate, p-aminobenzenesulfonic acid,potassium p-aminobenzenesulfonate, N-methylaniline,N-propyl-N-phenylaniline, N-methyl-N-2-propenylaniline, N-benzylaniline,N-(2-ethylphenyl)aniline, 4-methylaniline, 4-(2-bromoethyl)aniline,2-(2-nitroethyl)aniline, (4-aminophenyl)acetaldehyde,(4-aminophenyl)acetic acid, 4-(2-propenyl)aniline acetate,4-(3-bromo-2-propenyl)aniline, 4-phenylaniline chloroacetate,4-(3-chlorophenyl)aniline, 4-benzylaniline, 4-(4-iodobenzyl)aniline,4-(3-ethylphenyl)aniline, 4-(2-chloro-4-ethylphenyl)aniline.

[0119] wherein Z and R₇ are defined as in formula (IV) and R₈ ishydrogen or C₁ to C₄ substituted or unsubstituted alkyl or alkenylwherein the substituents are selected from those defined as Z in formula(IV).

[0120] Specific examples of formula (V) compounds are:

[0121] phenol, p-chlorophenol, p-nitrophenol, p-hydroxybenzaldehyde,p-hydroxybenzoic acid, p-hydroxybenzenesulfonic acid, ethylphenyl ether,2-chloroethylphenyl ether, 2-nitroethylphenyl ether,phenoxyacetaldehyde, phenoxyacetic acid, 3-phenoxy-1-propene,3-phenoxy-2-nitro-1-propene, 3-phenoxy-2-bromo-1-propene,4-propylphenol, 4-(3-bromopropvl)phenol, 2-(2-nitroethyl)phenol,(4-hydroxyphenyl)acetaldehyde, (4-hydroxyphenyl)acetic acid,4-(2-propenyl)phenol, 4-phenylphenol, 4-benzylphenol,4-(3-fluoro-2-propenyl)phenol, 4-(4-chlorobenzyl)phenol,4-(3-ethylphenyl)phenol, 4-(2-chloro-3-ethylphenyl)phenol, 2,5-xylenol,2,5-diaminopyridine, 2-hydroxy-5-aminopyridine, 2-amino-3-hydroxypyridine, tetraaminopyrimindine, 1,2,4-trihydroxybenzene,1,2,4-trihydroxy-5-(C₁-C₆-alkyl)benzene, 1,2,3-trihydroxybenzene,4-aminoresorcinol, 1,2-dihydroxybenzene, 2-amino-1,4-dihydroxybenzene,2-amino-4-methoxy-phenol, 2,4-diaminophenol,3-methoxy-1,2-dihydroxy-benzene,1,4-dihydroxy-2-(N,N-diethylamino)benzene,2,5-diamino-4-methoxy-1-hydroxybenzene,4,6-dimethoxy-3-amino-1-hydroxybenzene,2,6-dimethyl-4-[N-(p-hydroxyphenyl)amino]-1-hydroxybenzene,1,5-diamino-2-methyl-4-[N-(p-hydroxyphenyl)amino]benzene and saltsthereof.

[0122] In preferred compositions suitable for use herein the followingcombination of primary intermediates and couplers are excluded:

[0123] Where R₁ and R₂ are not H

[0124] in combination with m-aminophenol, resorcinol,2-methyl-5-aminophenol, 2-metylresorcinol and mixtures thereof.

[0125] Additional primary intermediates suitable for use herein includecatechol species and in particular catechol “dopa” species whichincludes dopa itself as well as homologs, analogs and derivatives ofDOPA. Examples of suitable cachetol species include cysteinyl dopa,alpha alkyl dopa having 1 to 4, preferably 1 to 2 carbon atoms in thealkyl group, epinephrine and dopa alkyl esters having 1 to 6 ,preferably 1 to 2 carbon atoms in the alkyl group.

[0126] In general suitable catechols are represented by formula (VI)below:

[0127] wherein R₁, R₂ and R₃, which may be the same or different, areelectron donor or acceptor substutuents selected from H, lower (C₁-C₆)alkyl, OH, OR, COOR, NHCOR, CN, COOH, Halogen, NO₂, CF₃, SO₃H or NR₄R₅,with the proviso that only one of the R₁, R₂ or R₃ can be CN, COOH,halogen, NO₂, CF₃ or SO₃H: R₄ and R₅, which may be the same ordifferent, are H, lower (C₁-C₆) alkyl or substituted lower (C₁-C₆) alkylin which the substituent may be OH, OR, NHCOR₆, NHCONH₂, NHCO₂R₆,NHCSNH₂, CN, COOH, SO₃H, SO₂NR₆, SO₂R₆ or CO₂R₆; R₆ is lower (C₁-C₆)alkyl, lower (C₁-C₆) hydroxyalkyl phenyl linked to the nitrogen by analkylene chain, phenyl or substituted phenyl with the substituentdefined as R₁, and R is C₁-C₆ alkyl or C₁-C₆ hydroxyalkyl.

[0128] Also included herein are oxidative hair coloring agents of theformula:

[0129] wherein: R₁=substituted or unsubstituted benzene ring,tertiary-butyl, etc.; R=substituted or unsubstituted benzene ring andthe formula:

[0130] wherein R=aminoalkyl, amidoalkyl, aminobenzene (substituted orunsubstituted), amidobenzene (substituted or unsubstituted), alkyl,substituted or unsubstituted benzene ring; R₁=substituted orunsubstituted benzene ring.

[0131] The primary intermediates can be used herein alone or incombination with other primary intermediates, and one or more can beused in combination with one or more couplers. The choice of primaryintermediates and couplers will be determined by the color, shade andintensity of coloration which is desired. There are nineteen preferredprimary intermediates and couplers which can be used herein, singly orin combination, to provide dyes having a variety of shades ranging fromash blonde to black; these are: pyrogallol, resorcinol,p-toluenediamine, p-phenylenediamine, o-phenylenediamine,m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol,nitro-p-phenylenediamine, N-phenyl-p-phenylenediamine, m-aminophenol,2-amino-3-hydroxypyridine, 1-napthol, N,N bis(2-hydroxyethyl)p-phenylenediamine, 4-amino-2-hydroxytoluene,1,5-dihydroxynapthalene, 2-methyl resorcinol and 2,4-diaminoanisole.These can be used in the molecular form or in the form ofperoxide-compatible salts, as detailed above.

[0132] The primary intermediates and coupling compounds asaforementioned herein may be combined to deliver a wide variety ofcolors to the hair. The hair colors can vary by both depth of color andintensity of color. As hereinbefore described the compositions accordingto the present invention are valuable for the provision of highintensity colors. Intensity of color as defined herein means thequantity of color compound formed on and retained in the hair. Ingeneral, high intensity as defined herein means dark or deep colors suchas dark red, dark brown or black etc. In accordance, with the above itis possible to formulate hair colors of varying color intensity byadjusting the initial levels of each of the oxidative dyeing materials.

[0133] For example low intensity colors such as natural blond to lightbrown hair shades generally comprise from about 0.001% to about 5%,preferably from about 0.1% to about 2%, more preferably from about 0.2%to about 1% by weight of coloring composition of total oxidative dyeingagents and may be achieved by the combination of primary intermediatessuch as 1,4-diamino-benzene, 2,5-diamino toluene, 2,5-diamino-anisole,4-aminophenol, 2,5-diamino-benzyl alcohol and2-(2′,5′-diamino)phenyl-ethanol with couplers such as resorcinol,2-methyl resorcinol or 4-chloro resorcinol.

[0134] Similarly combination of the above primary intermediates withcouplers, such as, 5-amino-2-methyl phenol and 1,3-diamino-benzenederivatives such as 2,4-diamino-anisole at levels of from about 0.5% toabout 1% of total dyeing agents can lead to medium intensity red colors.High intensity colors such as blue to blue-violet hair shades can beproduced by the combination of the above primary intermediates withcouplers such as 1,3-diamino-benzene or its derivatives such as2,5-diamino-toluene at levels of from about 1% to about 6% by weight ofcomposition of total dyeing agents. Black hair colors can be obtained bycombining the aforementioned primary intermediates with couplers such as1,3-diaminobenzene or its derivatives

[0135] However considerations have been raised against the physiologicalcompatibility of para-amino phenol which is commonly used to impart redcolors to the hair. Similarly, the physiological compatibility of someof the agents favoured for the production of black color such asparaphenylene diamine (PPD) has been called into question. Thus a needexists for oxidative hair coloring compositions which have an improvedsafety profile and in particular oxidative hair compositions for thedelivery of dark colors i.e. high color intensity dyes, which have animproved safety profile. As discussed herein before, the low pHcompositions of the present invention provide excellent hair coloringattributes in combination with reduced levels of hair damage and skinstaining and/or irritation.

[0136] As such the compositions according to the present invention arevaluable for the delivery of improved hair condition attributes incombination with good initial color development and consistency andimproved wash fastness over time in addition to having reduced levels ofhair damage and skin irritation and/or staining.

Non-oxidative and Other Dyes

[0137] The hair coloring compositions of the present invention may, inaddition to the essential oxidative hair coloring agents, optionallyinclude non-oxidative and other dye materials. Optional non-oxidativeand other dyes suitable for use in the hair coloring compositions andprocesses according to the present invention include bothsemi-permanent, temporary and other dyes. Non-oxidative dyes as definedherein include the so-called ‘direct action dyes’, metallic dyes, metalchelate dyes, fibre reactive dyes and other synthetic and natural dyes.Various types of non-oxidative dyes are detailed in: ‘Chemical andPhysical Behaviour of Human Hair’ 3rd Ed. by Clarence Robbins(pp250-259); ‘The Chemistry and Manufacture of Cosmetics’. Volume IV.2nd Ed. Maison G. De Navarre at chapter 45 by G. S. Kass (pp841-920);‘cosmetics: Science and Technology’ 2nd Ed., Vol. II Balsam Sagarin,Chapter 23 by F. E. Wall (pp 279-343); ‘The Science of Hair Care’ editedby C. Zviak, Chapter 7 (pp 235-261) and .‘Hair Dyes’, J. C. Johnson,Noyes Data Corp., Park Ridge, U.S.A. (1973), (pp 3-91 and 113-139).

[0138] Direct action dyes which do not require an oxidative effect inorder to develop the color, are also designated hair tints and have longbeen known in the art. They are usually applied to the hair in a basematrix which includes surfactant material. Direct action dyes includenitro dyes such as the derivatives of nitroamino benzene ornitroaminophenol; disperse dyes such as nitroaryl amines,aminoanthraquinones or azo dyes; anthraquinone dyes, naphthoquinonedyes; basic dyes such as Acridine Orange C.I. 46005.

[0139] Nitrodyes are added to dyeing compositions to enhance colour ofcolorant and to add suitable aesthetic colour to the dye mixture priorto application.

[0140] Further examples of direct action dyes include the Arianor dyesbasic brown 17, C.I.(color index)—no. 12,251; basic red 76, C.I.—12,245;basic brown 16, C.I.—12,250; basic yellow 57, C.I.—12,719 and basic blue99, C.I.—56,059 and further direct action dyes such as acid yellow 1,C.I.—10,316 (D&C yellow no.7); acid yellow 9, C.I.—13,015; basic violetC.I.—45,170; disperse yellow 3, C.I.—11,855; basic yellow 57,C.I.—12,719; disperse yellow 1, C.I.—10,345; basic violet 1,C.I.—42,535, basic violet 3, C.I.—42,555; greenish blue, C.I.—42090(FD&C Blue no.1); yellowish red, C.I.—14700 (FD&C red no.4); yellow,C.I.19140 (FD&C yellow no5); yellowish orange, C.I.15985 (FD&C yellowno.6); bluish green, C.I.42053 (FD&C green no.3); yellowish red,C.I.16035 (FD&C red no.40); bluish green, C.I.61570 (D&C green no.3);orange, C.I.45370 (D&C orange no.5); red, C.I.15850 (D&C red no.6);bluish red, C.I.15850(D&C red no.7); slight bluish red, C.1.45380(D&Cred no.22); bluish red, C.I.45410(D&C red no.28); bluish red,C.I.73360(D&C red no.30); reddish purple, C.I.17200(D&C red no.33);dirty blue red, C.I.15880(D&C red no.34); bright yellow red,C.I.12085(D&C red no.36); bright orange, C.I.15510(D&C orange no.4);greenish yellow, C.1.47005(D&C yellow no.10); bluish green,C.I.59040(D&C green no.8); bluish violet, C.I.60730(Ext. D&C violetno.2); greenish yellow, C.I.10316(Ext. D&C yellow no.7);

[0141] Fibre reactive dyes include the Procion (RTM), Drimarene (RTM),Cibacron (RTM), Levafix (RTM) and Remazol (RTM) dyes available from ICI,Sandoz, Ciba-Geigy, Bayer and Hoechst respectively.

[0142] Natural dyes and vegetable dyes as defined herein include henna(Lawsonia alba+L), camomile ( Matricaria chamomila or Anthemis nobilis),indigo, logwood and walnut hull extract.

[0143] Temporary hair dyes, or hair coloring rinses, are generallycomprised of dye molecules which are too large to diffuse into the hairshaft and which act on the exterior of the hair. They are usuallyapplied via a leave-in procedure in which the dye solution is allowed todry on the hair surface. As such these dyes are typically less resistantto the effects of washing and cleaning the hair with surface activeagents and are washed off of the hair with relative ease. Any temporaryhair dye may suitably be used in the compositions of the invention andexamples of preferred temporary hair dyes are illustrated below.

[0144] Semi-permanent hair dyes are dyes which are generally smaller insize and effect to temporary hair rinses but are generally larger thanpermanent (oxidative) dyes. Typically, semi-permanent dyes act in asimilar manner to oxidative dyes in that they have the potential todiffuse into the hair shaft. However, semi-permanent dyes are generallysmaller in size than the aforementioned conjugated oxidative dyemolecules and as such are pre-disposed to gradual diffusion out of thehair again. Simple hair washing and cleaning action will encourage thisprocess and in general semi-permanent dyes are largely washed out of thehair after about 5 to 8 washes. Any semi-permanent dye system may besuitably used in the compositions of the present invention. Suitablesemi-permanent dyes for use in the compositions of the present inventionare HC Blue 2, HC Yellow 4, HC Red 3, Disperse Violet 4, Disperse Black9, HC Blue 7, HC Yellow 2, Disperse Blue 3, Disperse violet 1 andmixtures thereof. Examples of semi-permanent dyes are illustrated below:

[0145] Typical semi-permanent dye systems incorporate mixtures of bothlarge and small color molecules. As the size of the hair is not uniformfrom root to tip the small molecules will diffuse both at the root andtip, but will not be retained within the tip, while the larger moleculeswill be generally only be able to diffuse into the ends of the hair.This combination of dye molecule size is used to help give consistentcolor results from the root to the tip of the hair both during theinitial dyeing process and during subsequent washing.

Buffering Agents

[0146] The coloring compositions of the present invention have a pH inthe range of from about 1 to about 6 , preferably from about 1.5 toabout 5.8, more preferably from about 1.8 to about 5.5, most preferablyfrom about 2 to about 5 and especially from about 3.5 to about 4.5.

[0147] As herein before described the pH of the preferred coloringcompositions of the present invention are maintained within the desiredpH range via the action of the inorganic peroxygen oxidising agent.However, if so desired, the compositions may contain one or moreoptional buffering agents and/or hair swelling agents (HSAs). Severaldifferent pH modifiers can be used to adjust the pH of the finalcomposition or any constituent part thereof.

[0148] This pH adjustment can be effected by using well known acidifyingagents in the field of treating keratinous fibres, and in particularhuman hair, such as inorganic and organic acids such as hydrochloricacid, tartaric acid, citric acid, succinic acid, phosphoric acid andcarboxylic or sulphonic acids such as ascorbic acid, acetic acid, lacticacid, sulphuric acid, formic acid, ammonium sulphate and sodiumdihydrogenphosphate/phosphoric acid, disodiumhydrogenphosphate/phosphoric acid, potassium chloride/hydrochloric acid,potassium dihydrogen phthalate/hydrochloric acid, sodiumcitrate/hydrochloric acid, potassium dihydrogen citrate/hydrochloricacid, potassium dihydrogencitrate/citric acid, sodium citrate/citricacid, sodium tartarate/tartaric acid, sodium lactate/lactic acid, sodiumacetate/acetic acid, disodium hydrogenphosphate/citric acid and sodiumchloride/glycine/hydrochloric acid, succinic acid and mixtures thereof.

[0149] Examples of alkaline buffering agents are ammonium hydroxide,ethylamine, dipropylamine, triethylamine and alkanediamines such as1,3-diaminopropane, anhydrous alkaline alkanolamines such as, mono ordi-ethanolamine, preferably those which are completely substituted onthe amine group such as dimethylaminoethanol, polyalkylene polyaminessuch as diethylenetriamine or a heterocyclic amine such as morpholine aswell as the hydroxides of alkali metals, such as sodium and potassiumhydroxide, hydroxides of alkali earth metals, such as magnesium andcalcium hydroxide, basic amino acids such as L-argenine, lysine,alanine, leucine, iso-leucine, oxylysine and histidine and alkanolaminessuch as dimethylaminoethanol and aminoalkylpropanediol and mixturesthereof. Also suitable for use herein are compounds that form HCO₃— bydissociation in water (hereinafter referred to as ‘ion formingcompounds’). Examples of suitable ion forming compounds are Na₂CO₃,NaHCO₃, K₂CO₃, (NH4)₂CO₃, NH₄HCO₃, CaCO₃ and Ca(HCO₃) and mixturesthereof.

[0150] Preferred for use herein as buffering agents are organic andinorganic acids having a first pKa below pH 6, and their conjugatebases. As defined herein, first pKa means, the negative logarithm (tothe base 10) of the equilibrium constant, K, where K is the aciddissociation constant. Suitable organic and inorganic acids for useherein are: aspartic, maleic, tartaric, glutamic, glycolic, acetic,succinic, salycilic, formic, benzoic, malic, lactic, malonic, oxalic,citric, phosphoric acid and mixtures thereof. Particularly preferred areacetic, succinic, salycilic and phosphoric acids and mixtures thereof.

[0151] The low pH coloring compositions according to the presentinvention, may, as will be described later herein, be comprised of afinal solution containing both peroxide and a oxidative hair coloringagents which have been admixed prior to application to the hair or asingle component system. As such, the compositions according to thepresent invention may comprise coloring kits of a number of separatecomponents.

[0152] In oxidising and coloring kits comprising a portion of inorganicperoxygen oxidising agent, such as hydrogen peroxide, which may bepresent in either solid or liquid form, a buffering agent solution canbe used to stabilise hydrogen peroxide. Since hydrogen peroxide isstable in the pH range from 2 to 4, it is necessary to use a bufferingagent having a pH within this range. Dilute acids are suitable hydrogenperoxide buffering agents.

[0153] In oxidising and coloring kits comprising an oxidising agent(which may be in solid or liquid form) in combination with one or morecoloring agents, a buffering agent capable of maintaining a solution pHin the range of from about 1 to about 6 , preferably from about 1.5 toabout 5.8, more preferably from about 1.8 to about 5.5, most preferablyfrom about 2 to about 5 and especially from about 3.5 to about 4.5. Assuch it is necessary to use a buffering agent having a pH within thisrange.

Catalyst

[0154] The coloring compositions herein may optionally contain atransition metal containing catalyst for the inorganic peroxygenoxidising agents and the, optional, preformed peroxy acid oxidisingagent(s). One suitable type of catalyst is a catalyst system comprisinga heavy metal cation of defined bleach catalytic activity, such ascopper, iron or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminiumcations, and a sequestrant having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243.

[0155] Other types of suitable catalysts include the manganese-basedcomplexes disclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. No.5,244,594. Preferred examples of these catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(PF₆)₂, Mn^(III)₂(u-O) 1 (u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄-(ClO₄)₂, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₃, andmixtures thereof. Others are described in EP-A-0,549,272. Other ligandssuitable for use herein include1,5,9-trimethyl-1,5,9-triazacyclododecane,2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane,1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

[0156] For examples of suitable catalysts see U.S. Pat. No. 4,246,612and U.S. Pat. No. 5,227,084. See also U.S. Pat. No. 5,194,416 whichteaches mononuclear manganese (IV) complexes such asMn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH₃)₃-(PF₆). Still anothertype of suitably catalyst, as disclosed in U.S. Pat. No. 5,114,606, is awater-soluble complex of manganese (III), and/or (IV) with a ligandwhich is a non-carboxylate polyhydroxy compound having at least threeconsecutive C—OH groups. Other examples include binuclear Mn complexedwith tetra-N-dentate and bi-N-dentate ligands, includingN₄Mn^(III)(u-O)₂Mn^(IV)N₄)⁺ and[Bipy₂Mn^(III)(u-O)₂Mn^(IV)bipy₂]-(ClO₄)₃.

[0157] Further suitable catalysts are described, for example, inEP-A-0,408,131 (cobalt complex catalysts), EP-A-0,384,503, andEP-A-0,306,089 (metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455(manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 andEP-A-0.224,952, (absorbed manganese on aluminosilicate catalyst), U.S.Pat. No. 4,601,845 (aluminosilicate support with manganese and zinc ormagnesium salt), U.S. Pat. No. 4,626,373 (manganese/ligand catalyst),U.S. Pat. No. 4,119,557 (ferric complex catalyst), DE-A-2,054,019(cobalt chelant catalyst) CA-A-866,191 (transition metal-containingsalts), U.S. Pat. No. 4,430,243 (chelants with manganese cations andnon-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganesegluconate catalysts).

Heavy Metal Ion Sequestrant

[0158] The coloring compositions of the invention may contain as anoptional component a heavy metal ion sequestrant. By heavy metal ionsequestrant it is meant herein components which act to sequester(chelate or scavenge) heavy metal ions. These components may also havecalcium and magnesium chelation capacity, but preferentially they showselectivity to binding heavy metal ions such as iron, manganese andcopper. Such sequestering agents are valuable in hair coloringcompositions as herein described for the delivery of controlledoxidising action as well as for the provision of good storage stabilityof the hair coloring products.

[0159] Heavy metal ion sequestrants are generally present at a level offrom about 0.005% to about 20%, preferably from about 0.01% to about10%, more preferably from about 0.05 % to about 2 % by weight of thecompositions.

[0160] Various sequestering agents, including the amino phosphonates,available as Dequest (RTM) from Monsanto, the nitriloacetates, thehydroxyethyl-ethylene triamines and the like are known for such use.Suitable heavy metal ion sequestrants for use herein include organicphosphonates, such as the amino alkylene poly (alkylene phosphonates),alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylenephosphonates.

[0161] Preferred among the above species are diethylene triamine penta(methylene phosphonate), ethylene diamine tri (methylene phosphonate)hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene1,1 diphosphonate.

[0162] Preferred biodegradable non-phosphorous heavy metal ionsequestrants suitable for use herein include nitrilotriacetic acid andpolyaminocarboxylic acids such as ethylenediaminotetracetic acid,ethylenetriamine pentaacetic acid, ethylenediamine disuccinic acid,ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinicacid or any salts thereof. Especially preferred isethylenediamine-N,N′-disuccinic acid (EDDS). see U.S. Pat. No.4,704,233, or the alkali metal, alkaline earth metal, ammonium, orsubstituted ammonium salts thereof, or mixtures thereof.

[0163] Other suitable heavy metal ion sequestrants for use herein areiminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid orglyceryl imino diacetic acid, described in EP-A-317,542 andEP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid andaspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acidsequestrants described in EP-A-516,102 are also suitable herein. Theβ-alanine-N,N′-diacetic acid, aspartic acid-N,N′-diacetic acid, asparticacid-N-monoacetic acid and iminodisuccinic acid sequestrants describedin EP-A-509,382 are also suitable.

[0164] EP-A-476,257 describes suitable amino based sequestrants.EP-A-510,331 describes suitable sequestrants derived from collagen,keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiaceticacid sequestrant. Dipicolinic acid and2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable.Glycinamide-N,N′-disuccinic acid (GADS), ethylenediamine-N-N′-diglutaricacid (EDDG) and 2-hydroxypropylenediamine-N-N′-disuccinic acid (HPDDS)are also suitable.

[0165] The heavy metal ion sequestering agents of the present inventionmay be used in their alkali or alkaline earth metal salts.

Thickeners

[0166] The coloring compositions of the present invention mayadditionally include a thickener at a level of from about 0.05% to about20%, preferably from about 0.1% to about 10%, more preferably from about0.5% to about 5% by weight. Thickening agents suitable for use in thecompositions herein are selected from oleic acid, cetyl alcohol, oleylalcohol, sodium chloride, cetearyl alcohol, stearyl alcohol, syntheticthickeners such as Carbopol, Aculyn and Acrosyl and mixtures thereof.Preferred thickeners for use herein are Aculyn 22 (RTM), steareth-20methacrylate copolymer; Aculyn 44 (RTM) polyurethane resin and Acusol830 (RTM), acrylates copolymer which are available from Rohm and Haas,Philadelphia, Pa., USA. Additional thickening agents suitable for useherein include sodium alginate or gum arabic, or cellulose derivatives,such as methyl cellulose or the sodium salt of carboxymethylcellulose oracrylic polymers.

Diluent

[0167] Water is the preferred diluent for the compositions according tothe present invention. However, the compositions according to thepresent invention may include one or more solvents as additional diluentmaterials. Generally, solvents suitable for use in the coloringcompositions of the present invention are selected to be miscible withwater and innocuous to the skin. Solvents suitable for use as additionaldiluents herein include C₁-C₂₀ mono- or polyhydric alcohols and theirethers, glycerine, with monohydric and dihydric alcohols and theirethers preferred. In these compounds, alcoholic residues containing 2 to10 carbon atoms are preferred. Thus, a preferred group includes ethanol,isopropanol, n-propanol, butanol, propylene glycol, ethylene glycolmonoethyl ether, and mixtures thereof. Water is the preferred principaldiluent in the compositions according to the present invention.Principal diluent, as defined herein, means, that the level of waterpresent is higher than the total level of any other diluents.

[0168] The diluent is present at a level preferably of from about 5% toabout 99.98%, preferably from about 15% to about 99.5%, more preferablyat least from about 30% to about 99%, and especially from about 50% toabout 98% by weight of the compositions herein.

Enzyme

[0169] A further additional material useful in the hair coloringcompositions according to the present invention is one or more enzymes.

[0170] Suitable enzymatic materials include the commercially availablelipases, cutinases, amylases, neutral and alkaline proteases, esterases,cellulases, pectinases, lactases and peroxidases conventionallyincorporated into detergent compositions. Suitable enzymes are discussedin U.S. Pat. Nos. 3,519,570 and 3,533,139.

[0171] Peroxidases are haemoproteins specific for peroxide, but using awide range of substances as donors. Catalase which decomposes peroxide,is included here in view of the fact that it is generally similar instructure and properties and is able to bring about certain oxidationsby H₂O₂. The decomposition of H₂O₂ can be regarded as the oxidation ofone molecule by the other. It is widespread in aerobic cells and mayhave some more important function. The coenzyme peroxidases are nothaemoproteins and one at least is a flavoprotein. Other flavoproteinssuch as xanthine oxidase will also use H₂O₂ among other acceptors, andthe coenzyme peroxidases resemble these rather than the classicalperoxidases in not being specific for H₂O₂. Suitable peroxidases for thecompositions of the present invention include horseradish peroxidase,Japanese radish peroxidase, cow's milk peroxidase, rat liver peroxidase,linginase and haloperoxidase such as chloro- and bromo-peroxidase.

[0172] Enzymes are optionally incorporated at levels sufficient toprovide up to about 50 mg by weight, more typically about 0.1 mg toabout 10 mg of active enzyme per gramm of the hair treatment compositionof the invention. Stated otherwise the peroxidase enzyme may beincorporated into the compositions in accordance with the invention at alevel of from about 0.0001% to about 5%, preferably from about 0.001% toabout 1%, more preferably from about 0.01% to about 1% active enzyme byweight of the composition.

[0173] Commercially available protease enzymes include those sold underthe trade names Alcalase, Savinase, Primase, Durazym, and Esperase byNovo Industries A/S (Denmark), those sold under the tradename Maxatase,Maxacal and Maxapem by Gist-Brocades, those sold by GenencorInternational, and those sold under the tradename Opticlean and Optimaseby Solvay Enzymes. Protease enzyme may be incorporated into thecompositions in accordance with the invention at a level of from 0.0001%to 4% active enzyme by weight of the composition.

[0174] Amylases include, for example, α-amylases obtained from a specialstrain of B licheniformis, described in more detail in GB-1,269,839(Novo). Preferred commercially available amylases include for example,those sold under the tradename Rapidase by Gist-Brocades, and those soldunder the tradename Termamyl and BAN by Novo Industries A/S. Amylaseenzyme may be incorporated into the composition in accordance with theinvention at a level of from 0.000 1% to 2% active enzyme by weight ofthe composition.

[0175] Lipolytic enzyme may be present at levels of active lipolyticenzyme of from 0.0001% to 2% by weight, preferably 0.001 % to 1% byweight, most preferably from 0.001 % to 0.5% by weight of thecompositions. The lipase may be fungal or bacterial in origin beingobtained, for example, from a lipase producing strain of Humicola sp.,Thermomyces sp. or Pseudomonas sp. including Pseudomonaspseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically orgenetically modified mutants of these strains are also useful herein. Apreferred lipase is derived from Pseudomonas pseudoalcalipenes, which isdescribed in Granted European Patent, EP-B-0218272.

[0176] Another preferred lipase herein is obtained by cloning the genefrom Humicola lanuginosa and expressing the gene in Aspergillus oryza,as host, as described in European Patent Application, EP-A-0258 068,which is commercially available from Novo Industri A/S, Bagsvaerd,Denmark, under the trade name Lipolase. This lipase is also described inU.S. Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.

Surfactant Materials

[0177] The compositions of the present invention can additionallycontain a surfactant system. Suitable surfactants for inclusion in thecompositions of the invention generally have a lipophilic chain lengthof from about 8 to about 22 carbon atoms and can be selected fromanionic, cationic, nonionic, amphoteric, zwitterionic surfactants andmixtures thereof.

[0178] (i) Anionic Surfactants

[0179] Anionic surfactants suitable for inclusion in the compositions ofthe invention include alkyl sulphates, ethoxylated alkyl sulphates,alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acylglycinates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates,alkyl ethoxysulphosuccinates, alpha-sulfonated fatty acids, their saltsand/or their esters, alkyl ethoxy carboxylates, alkyl phosphate esters,ethoxylated alkyl phosphate esters, alkyl sulphates, acyl sarcosinatesand fatty acid/protein condensates, and mixtures thereof. Alkyl and/oracyl chain lengths for these surfactants are C₁₂-C₂₂, preferably C₁₂-C₁₈more preferably C₁₂-C₁₄.

[0180] (ii) Nonionic Surfactants

[0181] The compositions of the invention can also comprise water-solublenonionic surfactant(s). Surfactants of this class include C₁₂-C₁₄ fattyacid mono-and diethanolamides, sucrose polyester surfactants andpolyhydroxy fatty acid amide surfactants having the general formulabelow.

[0182] The preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fattyacid amide surfactants according to the above formula are those in whichR₈ is C₅-C₃₁ hydrocarbyl, preferably C₆-C₁₉ hydrocarbyl, includingstraight-chain and branched chain alkyl and alkenyl, or mixtures thereofand R₉ is typically hydrogen, C₁-C₈ alkyl or hydroxyalkyl, preferablymethyl, or a group of formula —R¹—O—R² wherein R¹ is C₂-C₈ hydrocarbylincluding straight-chain, branched-chain and cyclic (including aryl),and is preferably C₂-C₄ alkylene, R² is C₁-C₈ straight-chain,branched-chain and cyclic hydrocarbyl including aryl and oxyhydrocarbyl,and is preferably C₁-C₄ alkyl, especially methyl, or phenyl. Z₂ is apolyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with atleast 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in thecase of other reducing sugars) directly connected to the chain, or analkoxylated derivative (preferably ethoxylated or propoxylated) thereof.Z₂ preferably will be derived from a reducing sugar in a reductiveamination reaction, most preferably Z₂ is a glycityl moiety. Suitablereducing sugars include glucose, fructose, maltose, lactose, galactose,mannose, and xylose, as well as glyceraldehyde. As raw materials, highdextrose corn syrup, high fructose corn syrup, and high maltose cornsyrup can be utilised as well as the individual sugars listed above.These corn syrups may yield a mix of sugar components for Z₂. It shouldbe understood that it is by no means intended to exclude other suitableraw materials. Z₂ preferably will be selected from the group consistingof —CH₂—(CHOH)_(n—CH) ₂OH, —CH(CH₂OH)—(CHOH)_(n-1)—CH₂H,CH₂(CHOH)₂(CHOR′)CHOH)—CH₂OH, where n is an integer from 1 to 5,inclusive, and R′ is H or a cyclic mono- or polysaccharide, andalkoxylated derivatives thereof. As noted, most preferred are glycitylswherein n is 4, particularly —CH₂—(CHOH)₄—CH₂OH.

[0183] The most preferred polyhydroxy fatty acid amide has the formulaR₈(CO)N(CH₃)CH₂(CHOH)₄CH₂OH wherein R₈ is a C6-C19 straight chain alkylor alkenyl group. In compounds of the above formula, R₈—CO—N< can be,for example, cocoamide, stearamide, oleamide, lauramide, myristamide,capricamide, palmiamide, tallowamide, etc.

[0184] Suitable oil derived nonionic surfactants for use herein includewater soluble vegetable and animal-derived emollients such astriglycerides with a polyethyleneglycol chain inserted; ethoxylated monoand di-glycerides, polyethoxylated lanolins and ethoxylated butterderivatives. One preferred class of oil-derived nonionic surfactants foruse herein have the general formula below:

O

RCOCH₂CH(OH)CH₂(OCH₂CH₂)_(n)OH

[0185] wherein n is from about 5 to about 200, preferably from about 20to about 100, more preferably from about 30 to about 85, and wherein Rcomprises an aliphatic radical having on average from about 5 to 20carbon atoms, preferably from about 7 to 18 carbon atoms.

[0186] Suitable ethoxylated oils and fats of this class includepolyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate,glyceryl caprylate, glyceryl tallowate, glyceryl palmate, glycerylstearate, glycervl laurate, glyceryl oleate, glyceryl ricinoleate, andglyceryl fatty esters derived from triglycerides, such as palm oil,almond oil, and corn oil, preferably glyceryl tallowate and glycerylcocoate.

[0187] Preferred for use herein are polyethyleneglycol basedpolyethoxylated C₉-C₁₅ fatty alcohol nonionic surfactants containing anaverage of from about 5 to about 50 ethyleneoxy moieties per mole ofsurfactant.

[0188] Suitable polyethylene glycol based polyethoxylated C₉-C₁₅ fattyalcohols suitable for use herein include C₉-C₁₁ Pareth-3, C₉-C₁₁Pareth4, C₉-C₁₁ Pareth-5, C₉-C₁₁ Pareth-6, C₉-C₁₁ Pareth-7, C₉-C₁₁Pareth-8, C₁₁-C₁₅ Pareth-3, C₁₁-C₁₅ Pareth-4, C₁₁-C₁₅ Pareth-5, C ₁₁-C₁₅Pareth-6, C₁₁-C₁₅ Pareth-7, C₁₁-C₁₅ Pareth-8, C₁₁-C₁₅ Pareth-9, C₁₁-C₁₅Pareth-10, C₁₁-C₁₅ Pareth-11, C₁₁-C₁₅ Pareth-12, C₁₁-C₁₅ Pareth-13 andC₁₁-C₁₅ Pareth-14. PEG 40 hydrogenated castor oil is commerciallyavailable under the tradename Cremophor (RTM) from BASF. PEG 7 glycerylcocoate and PEG 20 glyceryl laurate are commercially available fromHenkel under the tradenames Cetiol (RTM) HE and Lamacit (RTM) GML 20respectively. C₉-C₁₁ Pareth-8 is commercially available from Shell Ltdunder the tradename Dobanol (RTM) 91-8. Particulary preferred for useherein are polyethylene glycol ethers of ceteryl alcohol such asCeteareth 25 which is available from BASF under the trade name CremaphorA25.

[0189] Also suitable for use herein are nonionic surfactants derivedfrom composite vegetable fats extracted from the fruit of the Shea Tree(Butyrospermum Karkii Kotschy) and derivatives thereof. Similarly,ethoxylated derivatives of Mango, Cocoa and Illipe butter may be used incompositions according to the invention. Although these are classifiedas ethoxylated nonionic surfactants it is understood that a certainproportion may remain as non-ethoxylated vegetable oil or fat.

[0190] Other suitable oil-derived nonionic surfactants includeethoxylated derivatives of almond oil, peanut oil, rice bran oil, wheatgerm oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palmnuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peachpit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil,safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed oil, andsunflower seed oil.

[0191] (iii) Amphoteric Surfactants

[0192] Amphoteric surfactants suitable for use in the compositions ofthe invention include:

[0193] (a) imidazolinium surfactants of formula (VII)

[0194] wherein R₁ is C₇-C₂₂ alkyl or alkenyl, R₂ is hydrogen or CH₂Z,each Z is independently CO₂M or CH₂CO₂M, and M is H, alkali metal,alkaline earth metal, ammonium or alkanolammonium; and/or ammoniumderivatives of formula (VIII)

[0195] wherein R₁, R₂ and Z are as defined above;

[0196] (b) aminoalkanoates of formula (IX)

R₁NH(CH₂)_(n)CO₂M

[0197] iminodialkanoates of formula (X)

R₁N[(CH₂)_(m)CO₂M]₂

[0198] and iminopolyalkanoates of formula (XI)

[0199] wherein n, m, p, and q are numbers from 1 to 4, and R₁ and M areindependently selected from the groups specified above; and

[0200] (c) mixtures thereof.

[0201] Suitable amphoteric surfactants of type (a) are marketed underthe trade name Miranol and Empigen and are understood to comprise acomplex mixture of species. Traditionally, the Miranols have beendescribed as having the general formula (VII), although the CTFACosmetic Ingredient Dictionary, 3rd Edition indicates the non-cyclicstructure (VIII) while the 4th Edition indicates yet another structuralisomer in which R₂ is O-linked rather than N-linked. In practice, acomplex mixture of cyclic and non-cyclic species is likely to exist andboth definitions are given here for sake of completeness. Preferred foruse herein, however, are the non-cyclic species.

[0202] Examples of suitable amphoteric surfactants of type (a) includecompounds of formula XII and/or XIII in which R₁ is C₈H₁₇ (especiallyiso-capryl), C₉H₁₉ and C₁₁H₂₃ alkyl. Especially preferred are thecompounds in which R₁ is C₉H₁₉, Z is CO₂M and R₂ is H; the compounds inwhich R₁ is C₁₁H₂₃, Z is CO₂M and R₂ is CH₂CO₂M; and the compounds inwhich R₁ is C₁₁H₂₃, Z is CO₂M and R₂ is H.

[0203] In CTFA nomenclature, materials suitable for use in the presentinvention include cocoamphocarboxypropionate, cocoamphocarboxy propionicacid, and especially cocoamphoacetate and cocoamphodiacetate (otherwisereferred to as cocoamphocarboxyglycinate). Specific commercial productsinclude those sold under the trade names of Ampholak 7TX (sodium carboxymethyl tallow polypropyl amine), Empigen CDL60 and CDR 60 (Albright &Wilson), Miranol H2M Conc. Miranol C2M Conc. N. P., Miranol C2M Conc. O.P., Miranol C2M SF, Miranol CM Special (Rhône-Poulenc); Alkateric 2CIB(Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38,Monateric CSH-32 (Mona Industries); Rewoteric AM-2C (Rewo ChemicalGroup); and Schercotic MS-2 (Scher Chemicals). Further examples ofamphoteric surfactants suitable for use herein include Octoxynol-1(RTM), polyoxethylene (1) octylphenyl ether; Nonoxynol-4 (RTM),polyoxyethylene (4) nonylphenyl ether and Nonoxynol-9, polyoxyethylene(9) nonylphenyl ether.

[0204] It will be understood that a number of commerciallv-availableamphoteric surfactants of this type are manufactured and sold in theform of electroneutral complexes with, for example, hydroxidecounterions or with anionic sulfate or sulfonate surfactants, especiallythose of the sulfated C₈-C₁₈ alcohol, C₈-C₁₈ ethoxylated alcohol orC₈-C₁₈ acyl glyceride types. Note also that the concentrations andweight ratios of the amphoteric surfactants are based herein on theuncomplexed forms of the surfactants, any anionic surfactant counterionsbeing considered as part of the overall anionic surfactant componentcontent.

[0205] Examples of preferred amphoteric surfactants of type (b) includeN-alkyl polytrimethylene poly-, carboxymethylamines sold under the tradenames Ampholak X07 and Ampholak 7CX by Berol Nobel and also salts,especially the triethanolammonium salts and salts of N-lauryl-beta-aminopropionic acid and N-lauryl-imino-dipropionic acid. Such materials aresold under the trade name Deriphat by Henkel and Mirataine byRhône-Poulenc.

[0206] (iv) Zwitterionic Surfactants

[0207] Water-soluble auxiliary zwitterionic surfactants suitable forinclusion in the compositions of the present invention include alkylbetaines of the formula R₅R₆R₇N⁺ (CH₂)_(n)CO₂M and amido betaines of theformula (XII) below:

[0208] wherein R₅ is C₁₁-C₂₂ alkyl or alkenyl, R₆ and R₇ areindependently C₁-C₃ alkyl, M is H, alkali metal, alkaline earth metal,ammonium or alkanolammonium, and n, m are each numbers from 1 to 4.Preferred betaines include cocoamidopropyldimethylcarboxymethyl betaine,laurylamidopropyldimethylcarboxymethyl betaine and Tego betaine (RTM).

[0209] Water-soluble auxiliary sultaine surfactants suitable forinclusion in the compositions of the present invention include alkylsultaines of the formula (XIII) below:

[0210] wherein R₁ is C₇ to C₂₂ alkyl or alkenyl, R₂ and R₃ areindependently C₁ to C₃ alkyl, M is H, alkali metal, alkaline earthmetal, ammonium or alkanolammonium and m and n are numbers from I to 4.Preferred for use herein is coco amido propylhydroxy sultaine.

[0211] Water-soluble auxiliary amine oxide surfactants suitable forinclusion in the compositions of the present invention include alkylamine oxide R₅R₆R₇NO and amido amine oxides of the formula (XIV) below:

[0212] wherein R₅ is C₁₁ to C₂₂ alkyl or alkenyl, R₆ and R₇ areindependently C₁ to C₃ alkyl, M is H, alkali metal, alkaline earthmetal, ammonium or alkanolammonium and m is a number from 1 to 4.Preferred amine oxides include cocoamidopropylamine oxide, lauryldimethyl amine oxide and myristyl dimethyl amine oxide.

Optional Materials

[0213] A number of additional optional materials can be added to thecoloring compositions herein described each at a level of from about0.001% to about 5%, preferably from about 0.01% to about 3%, morepreferably from about 0.05% to about 2% by weight of composition. Suchmaterials include proteins and polypeptides and derivatives thereof;water-soluble or solubilizable preservatives such as DMDM Hydantoin,Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoicacid, EDTA, Euxyl (RTM) K400, natural preservatives such as benzylalcohol, potassium sorbate and bisabalol, benzoic acid, sodium benzoateand 2-phenoxyethanol; antioxidants such as sodium sulphite,hydroquinone, sodium bisulphite, sodium metabisulphite and thyoglycolicacid, sodium dithionite, erythrobic acid and other mercaptans; dyeremovers such as oxalic acid, sulphated castor oil, salicylic acid andsodium thiosulphate; H₂O₂ stabilisers such as tin compounds such assodium stannate, stannic hydroxide and stannous octoate, acetanilide,phenacetin colloidal silica such as magnesium silicate, oxyquinolinesulphate, sodium phosphate, and tetrasodium pyrophosphate; andp-hydroxybenzoates; moisturising agents such as hyaluronic acid, chitin, and starch-grafted sodium polyacrylates such as Sanwet (RTM) IM-1000,IM-1500 and IM-2500 available from Celanese Superabsorbent Materials,Portsmith, Va., USA and described in U.S. Pat. No. 4,076,663 as well asmethyl cellulose, starch, higher fatty alcohols, paraffin oils, fattyacids and the like; solvents ; anti-bacterial agents such as Oxeco(phenoxy isopropanol); low temperature phase modifiers such as ammoniumion sources (e.g. NH₄ Cl); viscosity control agents such as magnesiumsulfate and other electrolytes; quaternary amine compounds such asdistearyl-, dilauryl-, di-hydrogenated beef tallow-, dimethyl ammoniumchloride, dicetyldiethyl ammoniumethylsulphate, ditallowdimethylammonium methylsulphate, disoya dimethyl ammonium chloride and dicocodimethyl ammonium chloride; hair conditioning agents such as silicones,higher alcohols, cationic polymers and the like; enzyme stabilisers suchas water soluble sources of calcium or borate species; colouring agents;TiO₂ and TiO₂-coated mica; perfumes and perfume solubilizers; andzeolites such as Valfour BV400 and derivatives thereof and Ca²⁺/Mg²⁺sequestrants such as polycarboxylates, amino polycarboxylates,polyphosphonates, amino polyphosphonates etc. and water softening agentssuch as sodium citrate.

[0214] The present invention is represented by the followingnon-limiting examples. In the examples, all concentrations are on a 100%active basis and all percentages are by weight unless otherwise statedand the abbreviations have the following designations: Oxidising agenthydrogen peroxide Oxidative Dye 1 para-phenylene diamine Oxidative Dye 2para-aminophenol Oxidative Dye 3 meta-aminophenol Oxidative Dye 42-amino-3-hydroxy pyridine Oxidative Dye 5 4-amino-2-hydroxy tolueneNon-oxidative Dye Basic red 76 Chelating agent Ethylenediaminetetraaceticacid Surfactant 1 Ceteareth-25 Surfactant 2 Cocoamidopropylbetaine Thickener 1 Cetyl alcohol Thickener 2 Stearyl alcoholAntioxidant Sodium sulphite Buffering Agent 1 Acetic acid

EXAMPLES I-VII

[0215] The following are hair treatment compositions in the form of haircoloring compositions which are representative of the present invention.Ingredient I II III IV V VI VII Oxidising Agent 0.7 0.7 0.7 0.7 0.7 2.51.5 Oxidative Dye 1 0.24 0.14 0.24 0.15 0.24 0.4 0.4 Oxidative Dye 20.09 0.05 0.009 0.5 0.09 0.1 0.1 Oxidative Dye 3 0.006 0.004 0.006 —0.006 — — Oxidative Dye 4 0.06 0.03 0.06 0.1 0.06 0.06 0.06 OxidativeDye 5 — — — 0.5 — — — Non-Oxidative Dye — — — — — 0.1 — Surfactant 1 1.51.7 1.5 1.5 1.5 1.5 — Surfactant 2 — — — — — — 1.5 Chelating agent 0.10.06 0.09 0.2 0.1 0.1 0.1 Thickener 1 2.3 2.6 2.3 2.3 2.3 4.0 4.0Thickener 2 2.3 2.6 2.3 2.3 2.3 2.0 2.0 Antioxidant 0.1 0.06 0.1 0.2 0.10.1 0.1 Buffer 1 — — — 0.5 0.5 0.2 0.2 Water to balance pH 4.0 3.8 3.94.6 2.7 — —

[0216] In the examples, water is used as the diluent. However invariations hereof water can be replaced, in part, by from about 0.5% toabout 50% by weight of the total water content of the examples bydiluents such as lower alcohols, e.g., ethylene glycol, ethylene glycolmonoethyl ether, diethylene glycol, diethylene glycol monoethyl ether,propylene glycol, 1,3-propane diol, ethanol, isopropyl alcohol,glycerine, butoxyethanol, ethoxydiglycol, hexylene glycol,polyglyceryl-2-oleyl ether and mixtures thereof.

Experimental Methods

[0217] I Assessment of Initial Color and Color Change

[0218] The equipment used to measure both the initial color and colorchange on substrates (hair/skin) dyed with the low pH coloringcompositions of the present invention is a Hunter Colorquestspectrophotometer. The value used to express the degree of color changeon any particular substrate is Delta E (^(Δ)E). Delta E, as definedherein, is represented by a factual sum of L, a, and b values such that:

^(Δ) E=(^(Δ) L ²+^(Δ) a2+^(Δ) _(b)2)½

[0219] and L is a measure of lightness and darkness (color intensity),wherein L=100 is equivalent to white, and L=0 is equivalent to black.Further, ‘a’ is a measure of the red and green quotients (color hues)such that positive equates to red and negative equates to green, and ‘b’is a measure of the yellow and blue quotients (color hues) such thatpositive equates to yellow and negative equates to blue.

[0220] Hunter Colorquest measurements can be carried out on the HunterLabscan Colorimeter which is full scanning spectrocolorimeter with awavelength of from 400-700 nanometers which records the color of testhair switches (tresses) in terms of ‘L’, ‘a’ and ‘b’ values. The machineis set to: mode—0/45; port size—1 inch; view size—1 inch; light—D65;field of view—10°; UV lamp/filter—none. The hair is placed in a sampleholder designed to hold the hair in a uniform orientation duringmeasurement. Equivalent calorimeters can be used, but it must be ensuredthat the hair does not move during measurement. The hair must be spreadto cover the 1 inch port during color measurement. Dots are placed onthe switch holder to guide the positioning of the holder at the port.The dots are lined up with a mark on the port and readings are taken ateach spot.

[0221] Eight measurements are run per switch, 4 on each side, and threeswitches are run per treatment.

[0222] II. Standard Hair Switch

[0223] The compositions according to the present invention can be usedto color hair of all colors, types and condition. For the purposes ofillustration two test hair switch types; light brown and light brownwith 40% grey coverage have been tested herein. These standard hairswitches can be measured in terms of their approximate L, a, b values. La b Light brown 60 9 32 40% grey light brown 35-37 4.5-5.5 11.5-12.7

[0224] III Hair Switch Coloring Method

[0225] To color hair, a 4 gramme switch of about 8 inch long hair ishung over a suitable container. The test coloring product is thenprepared (i.e., where applicable the separate bottle components aremixed together) and about 8 grammes of product is applied directly tothe test hair switch. The colorant is massaged through the hair switchfor up to about 1 minute and then left on the hair switch for up toabout 30 minutes. After rinsing with running water for about 1 or 2minutes the colored hair switch is then cleansed (according to theshampoo protocol) and dried. Drying can be effected either naturally(without heat assistance) or using a drier. The color development(initial color) of the colored, cleansed, dried test hair switch canthen be assessed using the Hunter Colorquest spectrophotometer.

[0226] For the delivery of a red shade (hue) to prepermed, prebleachedlight brown hair (having L, a, b values of approximately 60, 9 and 32)the preferred initial shade of the colored hair will have a hue value(arc tangent of (b/a)) in the range of from about 25 to about 70, morepreferably from about 30 to about 65, most preferably from about 35 toabout 60 and wherein the initial color intensity (L) is greater thanabout 10 and less than about 70, preferably greater than about 15 andless than about 65, more preferably greater than about 20 and less thanabout 60.

[0227] For the delivery of a brown or black shade (hue) to preperned,prebleached light brown hair (having L, a, b values of approximately 60,9 and 32) the preferred initial shade of the colored hair will have ahue value (arc tangent of (b/a)) of less than about 25, preferably lessthan about 20 and the initial color intensity (L) will be greater thanabout 1 and less than about 50, preferably greater than about 5 and lessthan about 45.

[0228] For the delivery of a light brown shade (hue) to prepermed,prebleached light brown hair (having L, a, b values of approximately 60,9 and 32) the preferred initial shade of the colored hair will have ahue value (arc tangent of (b/a)) in the range of from about 70 up toabout 110 and wherein the initial color intensity (L) will be greaterthan about 20 and less than about 95, preferably greater than about 25and less than about 90.

[0229] A significant color change, as delivered via the coloringcompositions according to the present invention, means a color change interms of Delta E which is greater than about 8, preferably greater thanabout 10, more preferably greater than about 12, most preferably greaterthan about 15 and especially greater than about 20.

[0230] Hair Switch Cleansing Method

[0231] Switches of colored hair are subjected to a repeated cleansingcycle wherein the following process is repeated up to 10 times.

[0232] A 4 gramme, 8 inch test switch of colored hair is clamped over asuitable container and rinsed thoroughly for about 10 seconds using warmwater (at about 100° F. at about 1.5 gallons/minute pressure). Shampoo(about 0.4 ml non-conditioning shampoo) can then be applied directly tothe wet test switch using a syringe. After lathering the hair for about30 seconds the hair is rinsed in running warm water for about 30seconds. The shampoo and lathering process is then repeated with a final60 second rinse. Excess water can be removed (squeezed) from the testswitch using the fingers. The test switch is then dried eithernatrually, or using a pre-heated dryer box at about 140° F. (for about30 minutes). The colored, cleansed, dried test hair switch can then becolor assessed (Delta E fade).

[0233] During any single test cycle each different switch to be assessedshould be tested in water of equivalent temperature, pressure level andhardness level.

[0234] Delta E fade results for prepermed, prebleached light brown hair(having L, a, b values of approximately 60, 9 and 32) which has beencolored a red shade (of hue value in the range of from about 25 to about70) are generally less than about 5.0, preferably less than about 4.5,more preferably less than about 4.0 and wherein the change in haircolor, % delta E, after up to 20 washes, is less than about 20%, andpreferably less than about 15%, more preferably less than about 10%.

[0235] Delta E fade results for prepermed, prebleached light brown hair(having L, a, b values of approximately 60, 9 and 32) which has beencolored a brown or black shade (of hue value of less than about 25) aregenerally less than about 2.3, preferably less than about 2.0, morepreferably less than about 1.7 and wherein the change in hair color, %delta E, after up to 20 washes, is less than about 5%, preferably lessthan about 4.5%, more preferably less than about 4%, most preferablyless than about 3.5%.

[0236] Delta E fade results for preperned, prebleached light brown hair(having L, a, b values of approximately 60, 9 and 32) which has beencolored a light brown shade (of hue value in the range of from about 70to about 110) are generally less than about 2.6, preferably less thanabout 2.3 and wherein the change in hair color, % delta E, after up to20 washes, is less than about 15%, preferably less than about 12%, morepreferably less than about 10%, most preferably less than about 8%.

[0237] In preferred compositions herein, the change in the color of thedyed hair over time (Delta E fade) is less than about 15%, preferablyless than about 12%, more preferably less than about 10% and mostpreferably less than about 8%.

[0238] V Skin Staining Test Method

[0239] For the purposes of the present invention skin staining resultsare based on pig skin data.

[0240] Skin staining measurements can be made on pigs ears, preferablythe ears of recently deceased pigs. The ears should not have beensubject to undue heating (scalding). Hair is shaved from the most flatsection of the ear to be stained. An area of at least 1 cm×5cm ispre-marked on the ear (using a pernenant marker) and the ear is thencleansed with non-conditioning shampoo (0.1 g/cm² at 10% dilution).After massaging in the shampoo for about 1 minute the ear is rinsed forabout 30 seconds then gently patted dry by hand with a paper towel.Baseline color assessment readings (L, a, b) are then taken for thepre-marked area. The test dye is then applied to the pre-marked testarea (about 0.25 g/cm²) and massaged in for about 1 minute and allowedto remain on the ear for about 30 minutes. The colored ear is thenrinsed with about 2 liters of tap water at about 37° C. and hand driedas above. Color assessment readings (L, a, b) are then taken for thepre-marked area of the dyed ear. Total color change (Delta E) can thenbe calculted from the L, a, b values and expressed as relative levels ofskin staining (versus the baseline color).

[0241] VI Measurement of pH

[0242] For the purposes of the present invention, as described herein,all pH measurements were carried out on a Mettler Toledo 320 pH meter.All pH measurements of dyes, oxidising agents and mixtures thereof,either singly or in combination with a suitable delivery medium, such aswater and surfactant and /or thickeners, were carried out at roomtemperature (about 25° C.). The pH of dye mixtures were measured in theform of intended use and prior to application.. A preferred deliverymedium for use herein comprises an emulsion of ceteareth-25 at a levelof from about 1% to about 3% by weight, cetyl alohol at a level of fromabout 2% to about 5% by weight and stearyl alcohol at a level of fromabout 2% to about 5% of solution or composition.

Experimental Data

[0243] I Initial Color and Wash Fastness

[0244] Example formula I provides improved initial color and faderesistance versus a similar composition having pH outside the scope ofthe present invention.

[0245] Example formula II provides improved intial color development andwashfastness versus a similar high pH formula containing the same levelof oxidant and up to 60% more dye.

[0246] Example formula III provides improved initial color developmentversus a high pH formula containing the same level of dye but moreinorganic peroxygen oxidising agent.

[0247] II Relative Skin Staining

[0248] Example formula IV provides reduced levels of skin staining on apigs ear versus an equivalent composition at high pH.

[0249] Method of Manufacture

[0250] It is important that dyeing compositions be in a form which iseasy and convenient to prepare and use by the consumer, since theoxidising agent must remain in contact with the hair for a certainperiod of time and not run or drip off of the hair, possibly causing eyeor skin irritation.

[0251] To address the above, the coloring compositions of the presentinvention can be provided in both a single pack or in kit form asseparately packaged components to maintain stability, and, if sodesired, either mixed by the user immediately prior to application tothe hair, or mixed and stored for future use, or mixed and partly usedand the remainder stored for future use.

[0252] As hereinbefore described, the compositions according to thepresent invention may be used by the consumer as a single componentpackage. Such a single pack would comprise a single solution at pH 1 to6 containing both the inorganic peroxygen oxidising agent and theoxidative dye precursors. The solution would be applied directly to thehair by the consumer without the need for any pretreatments or mixingthereby providing a simple, fast, easy to use, ‘no-mess’ hair coloringsystem. A further advantage of such a single component system is that itcould be stored and re-used i.e., a single package could contain enoughcoloring composition for several applications over time.

[0253] Thus, according to a further aspect of the present invention,there is provided:

[0254] A method for coloring hair wherein a hair coloring mixture ispresent in a single package and applied directly to the hair and whereinthe hair coloring mixture comprises:

[0255] (a) from about 0.0003 moles (per 100 g of composition) to lessthan about 0.09 moles (per 100 g of composition) of an inorganicperoxygen oxidising agent; and

[0256] (b) an oxidative hair coloring agent; and

[0257] wherein the pH of each of (a) and (b), when in solution, is inthe range of from about 1 to about 6 and wherein the combined mixture of(a) and (b), when in solution, has a pH in the range of from about 1 toabout 6.

[0258] According to a still further aspect of the present invention,there is provided:

[0259] A method for coloring hair wherein a hair coloring composition ispresent as separately packaged components (a) and (b) and wherein thehair coloring composition comprises:

[0260] (a) from about 0.0003 moles (per 100 g of composition) to lessthan about 0.09 moles (per 100 g of composition) of an inorganicperoxygen oxidising agent wherein the pH of (a), is in the range of fromabout 1 to about 6; and

[0261] (b) an oxidative hair coloring agent wherein the pH of (b), is inthe range of from about 1 to about 6;

[0262] wherein each of (a) and (b) are stable at pHs in the range offrom about 1 to about 6 and wherein the combined mixture of (a) and (b)is stable over time and has a pH in the range of from about 1 to about6.

[0263] Alternatively the compositions according to the present inventioncan be packaged as follows: one component of the kit comprises anindividually packaged oxidising component while further kit componentscould comprise coloring agent mixture and, optionally, individuallypackaged additional, optional, oxidising agent(s), or two separateindividual packages of oxidising agent(s) and coloring agents. In oneembodiment of the present invention the oxidising component comprises astabilised aqueous solution of an inorganic peroxygen oxidising agent,most generally hydrogen peroxide in an amount such that the finalconcentration of the coloring composition for use on the hair is fromabout 0.05% to about 6% by weight and additional agents as herein beforedescribed. The compositions can either be mixed by the user immediatelyprior to application to the hair or can be applied separately. Examplesof such kits are as follows:

[0264] I. A hair coloring kit is assembled comprising a single packageincluding therein: (1) a 50 ml bottle of hydrogen peroxide (1.4% byweight of H₂O₂), and optionally buffering agents and/or stabilisers; and(2) a 50 ml bottle containing one or more oxidative hair coloring agentsand, optionally, additional agents such as surfactants, stabilisers,buffering agents, antioxidants, thickeners etc. The oxidative haircoloring agents can either be admixed with the hydrogen peroxide to formthe low pH dyeing system of the present invention and the resultingsolution can be either applied to the hair to color it or stored forfuture use, or the separately packaged stable components can be storedand mixed when required.

[0265] II. A hair coloring kit as described above wherein the hydrogenperoxide containing component is applied to the hair prior toapplication of the oxidative hair coloring agents and additionalmaterials to the hair.

[0266] III. Further examples of kit components for the hair coloringcompositions according to the present invention include separatelypackaged oxidant and oxidative hair coloring agents wherein either oneor both components are present in particulate form.

[0267] Method of Use

[0268] The compositions herein described are used to color hair. Thecoloring compositions herein are applied to the hair for periods of from1 minute to 60 minutes depending upon the degree of coloring required. Apreferred time is between 5 minutes and 30 minutes. The coloringcompositions according to the present invention can be applied to bothwet and dry hair.

[0269] As hereinbefore described the coloring composition can be presentas a single package, at low pH, suitable for direct application to thehair. Alternatively, the coloring composition can be present in kit formwherein one component comprises an oxidising agent and a furthercomponent comprises oxidative hair coloring agents. Hair coloring kitsaccording to the present invention can be used to color the hair inseveral ways including:

[0270] (i) the kit components are admixed to form a low pH coloringcomposition prior to application to the hair.

[0271] (ii) the hair oxidising agent is applied to the hair prior toapplication of the oxidative hair coloring agents.

[0272] (iii) the oxidative hair coloring agents are applied to the hairprior to application of the oxidising agent.

[0273] The products provide excellent initial hair coloring and in-useefficacy benefits including improved washfastness, color saturation andreduced hair damage at lower pH.

What is claimed is:
 1. A hair coloring composition comprising: (a) fromabout 0.0003 moles (per 100 g of composition) to less than about 0.09moles (per 100 g of composition) of an inorganic peroxygen oxidisingagent; and (b) an oxidative hair coloring agent; wherein the pH of eachof (a) and (b) is in the range of from about pH 1 to 6 and wherein thepH of the composition is in the range of from about 1 to about
 6. 2. Acomposition according to claim 1 wherein the pH of the composition is inthe range of from about 1.5 to about 5.8, preferably from about 1.8 toabout 5.5, more preferably from about 2 to about 5, most preferably fromabout 3.5 to about 4.5.
 3. A composition according to claim 1 or 2wherein the inorganic peroxygen oxidising agent is present at a molarlevel of from about 0.0003 moles (per 100 g of composition) to about0.08 moles (per 100 g of composition), preferably from about 0.0003moles to about 0.06 moles, more preferably from about 0.0003 moles toabout 0.04 moles, most preferably from about 0.0003 moles to about 0.03moles, especially from about 0.0003 moles to about 0.02 moles and mostespecially from about 0.0003 moles to about 0.015 moles (per 100 g ofcomposition).
 4. A composition according to any of claims 1 to 3 whereinthe inorganic peroxygen oxidising agent is present at a level of fromabout 0.01% to less than about 3%, preferably from about 0.01% to about2.5%, more preferably from about 0.01% to about 2%, even more preferablyfrom about 0.01% to about 1%, most preferably from about 0.01% to about0.8%, especially from about 0.01% to about 0.55% and especially fromabout 0.01% to about 0.5% by weight of the total composition.
 5. Acomposition according to any of claims 1 to 4 wherein the inorganicperoxygen oxidising agent is hydrogen peroxide.
 6. A compositionaccording to any of claims 1 to 5 wherein the total combined level ofoxidative hair coloring agent is from about 0.001% to about 5%,preferably from about 0.01% to about 4%, more preferably from about 0.1%to about 3%, most preferably from about 0.1% to about 1% by weight.
 7. Acomposition according to any of claims 1 to 6 wherein each oxidativehair coloring agent is present at a level of from about 0.001% to about3%, preferably from about 0.01% to about 2% by weight.
 8. A compositionaccording to any of claims 1 to 7 additionally comprising a preformedorganic peroxy acid oxidising agent.
 9. A composition according to claim8 wherein the preformed organic peroxy acid is present at a molar levelof from about 0.0001 moles to about 0.1 moles (per 100 g ofcomposition), more preferably from about 0.001 moles to about 0.05moles, most preferably from about 0.003 moles to about 0.04 moles andespecially from about 0.004 moles to about 0.03 moles per 100 g of thehair coloring composition.
 10. A composition according to claim 9wherein the preformed organic peroxy acid is present at a level of fromabout 0.01% to about 8%, preferably from about 0.1% to about 6%, morepreferably from about 0.2% to about 4% and most preferably from about0.3% to about 3% by weight and wherein the weight ratio of the inorganicoxidising agent:the organic oxidising agent is in the range of fromabout 0.00125:1 to about 500:1, preferably from about 0.0125:1 to about50:1.
 11. A composition according to any of claims 1 to 10 additionallycomprising one or more buffering agents, preferably an organic and/ororganic acid having a first pKa below pH 6, selected from: aspartic,maleic, tartaric, glutamic, glycolic, acetic, succinic, salycilic,formic, benzoic, malic, lactic, malonic, oxalic, citric, phosphoric acidand mixtures thereof, more preferably selected from acetic, succinic,salycilic and phosphoric acids and mixtures thereof.
 12. A compositionaccording to any of claims 1 to 11 additionally comprising one or moresurfactants selected from anionic, nonionic, cationic, zwitterionic,amphoteric surfactants and mixtures thereof.
 13. A composition accordingto any of claims 1 to 12 additionally comprising thickening agents,stabilisers, antioxidants and/or any other cosmetically acceptablematerial.
 14. Use of a composition according to any of claims 1 to 13for coloring human or animal hair.
 15. A process for coloring human oranimal hair wherein the hair coloring composition comprises: (a) fromabout 0.0003 moles (per 100 g of composition) to less than about 0.09moles (per 100 g of composition) of an inorganic peroxygen oxidisingagent; (b) an oxidative hair coloring agent; and (c) a diluent suitablefor application to the hair. wherein the coloring composition has a pHof from about 1 to about
 6. 16. A hair coloring kit comprising anindividually packaged oxidising component and an individually packagedcoloring component, wherein the oxidising component comprises an aqueoussolution of an inorganic peroxygen oxidising agent at a molar level offrom about 0.0003 moles (per 100 g of composition) to less than about0.09 moles (per 100 g of composition) having a pH in the range of fromabout 1 to about 6, and the coloring component comprises an oxidativehair coloring agent, capable of delivering a solution pH in the range offrom about 1 to about 6, and wherein the pH of the combined oxidisingagent and coloring components is in the range of from about 1 to about6.
 17. Use of a hair coloring kit according to claim 16 for theoxidising and coloring of hair wherein the inorganic oxidising agent,oxidative hair coloring agents and additional agents are admixed priorto application to the hair.
 18. A method for coloring hair wherein ahair coloring mixture is applied directly to the hair and wherein thehair coloring mixture comprises: (a) an inorganic peroxygen oxidisingagent at a molar level of from about 0.0003 moles (per 100 g ofcomposition) to less than about 0.09 moles (per 100 g of composition)having a pH in the range of from about 1 to about 6; and (b) anoxidative hair coloring agent at a pH of from about 1 to 6; wherein thecombined mixture of (a) and (b) has a pH in the range of from about 1 toabout 6, preferably from about 1.5 to 5.8, more preferably from about 2to about 5 and especially from about 3.5 to about 4.5.
 19. A haircoloring composition suitable for the delivery of a red shadecomprising: (a) an inorganic peroxygen oxidising agent at a molar levelof from about 0.0003 moles (per 100 g of composition) to less than about0.09 moles (per 100 g of composition) having a pH in the range of fromabout 1 to about 6; and (b) an oxidative hair coloring agent at a pH offrom about 1 to 6; wherein the change in hair color, delta E, is lessthan about 5 after 20 washes.
 20. A hair coloring composition suitablefor the delivery of a light brown shade comprising: (a) an inorganicperoxygen oxidising agent at a molar level of from about 0.0003 moles(per 100 g of composition) to less than about 0.09 moles (per 100 g ofcomposition) having a pH in the range of from about 1 to about 6; and(b) an oxidative hair coloring agent at a pH of from about 1 to 6;wherein the change in hair color, delta E, is less than about 2.6 after20 washes.
 21. A hair coloring composition suitable for the delivery ofa brown or black shade comprising: (a) an inorganic peroxygen oxidisingagent at a molar level of from about 0.0003 moles (per 100 g ofcomposition) to less than about 0.09 moles (per 100 g of composition)having a pH in the range of from about 1 to about 6; and (b) anoxidative hair coloring agent at a pH of from about 1 to 6; wherein thechange in hair color, delta E, is less than about 2.3 after 20 washes.22. A hair coloring composition, comprising an inorganic peroxygenoxidising agent and an oxidative hair coloring agent wherein the changein hair color, Delta E, is greater than about 8, preferably greater thanabout 10, more preferably greater than about 12, especially greater thanabout 15 and most especially greater than about 20, and wherein thechange in hair color over time (of the colored hair), % Delta E (fade)is less than about 15%, preferably less than about 12%, more preferablyless than about 10%,-and especially less than about 8% after 20 washes.23. A process capable of delivering a red shade to hair comprising:application to the hair of a composition according to claim 1comprising: (i) an inorganic peroxygen oxidising agent at a molar levelof from about 0.0003 moles (per 100 g of composition) to less than about0.09 moles (per 100 g of composition) having a pH in the range of fromabout 1 to about 6; and (ii) an oxidative hair coloring agent at a pH offrom about 1 to 6; wherein the untreated hair is prepermed, prebleachedlight brown hair having L, a, b values of approximately 60, 9 and 32 andwherein the initial shade of the colored hair has a hue value (arctangent of (b/a)) in the range of from about 25 to about 70, preferablyfrom about 30 to about 65, more preferably from about 35 to about 60 andwherein the initial color intensity (L) is greater than about 10 andless than about 70, preferably greater than about 15 and less than about65, more preferably greater than about 20 and less than about 60 andwherein the delta E fade is less than about 5.0, preferably less tha nabout 4.5, more preferably less than about 4.0 and wherein the change inhair color, % delta E, after up to 20 washes, is less than about 20%,and preferably less than about 15%, more preferably less than about 10%.24. A process capable of delivering a brown or black shade to haircomprising: application to the hair of a composition according to claim1 comprising: (i) an inorganic peroxygen oxidising agent at a molarlevel of from about 0.0003 moles (per 100 g of composition) to less thanabout 0.09 moles (per 100 g of composition) having a pH in the range offrom about 1 to about 6; and (ii) an oxidative hair coloring agent at apH of from about 1 to 6; wherein the untreated hair is prepermed,prebleached light brown hair having L, a, b values of approximately 60,9 and 32 and wherein the initial shade of the colored hair has a huevalue (arc tangent of (b/a)) of less than about 25, preferably less thanabout 20 and wherein the initial color intensity (L) is greater thanabout 1 and less than about 50, preferably greater than about 5 and lessthan about 45 and wherein the delta E fade is less than about 2.3,preferably less than about 2.0, more preferably less than about 1.7 andwherein the change in hair color, % delta E, after up to 20 washes, isless than about 5%, preferably less than about 4.5%, more preferablyless than about 4%, most preferably less than about 3.5%.
 25. A processcapable of delivering a light brown shade to hair comprising:application to the hair of a composition according to claim 1comprising: (i) an inorganic peroxygen oxidising agent at a molar levelof from about 0.0003 moles (per 100 g of composition) to less than about0.09 moles (per 100 g of composition) having a pH in the range of fromabout 1 to about 6; and (ii) an oxidative hair coloring agent at a pH offrom about 1 to 6; wherein the untreated hair is prepermed, prebleachedlight brown hair having L, a, b values of approximately 60, 9 and 32 andwherein the initial shade of the colored hair has a hue value (arctangent of (b/a)) in the range of from about 70 up to about 110 andwherein the initial color intensity (L) is greater than about 20 andless than about 95, preferably greater than about 25 and less than about90 and wherein the delta E fade is less than about 2.6, preferably lessthan about 2.3 and wherein the change in hair color, % delta E, after upto 20 washes, is less than about 15%, preferably less than about 12%,more preferably less than about 10%, most preferably less than about 8%.26. A method for coloring hair at a pH in the range of from about 1 toabout 6 comprising application to the hair of a composition according toclaim 1 comprising: (a) an inorganic peroxygen oxidising agent at amolar level of from about 0.0003 moles (per 100 g of composition) toless than about 0.09 moles (per 100 g of composition) having a pH in therange of from about 1 to about 6; and (b) an oxidative hair coloringagent at a pH of from about 1 to 6; (c) a diluent suitable forapplication to the hair; and wherein the combined pH of (a) and (b) isin the range of from about pH 1 to about pH
 6. 27. A method for coloringhair at a pH in the range of from about 1 to about 6 comprisingapplication to the hair of a composition according to claim 1comprising: (a) an inorganic peroxygen oxidising agent at a molar levelof from about 0.0003 moles (per 100 g of composition) to less than about0.09 moles (per 100 g of composition) having a pH in the range of fromabout 1 to about 6; and (b) an oxidative hair coloring agent at a pH offrom about 1 to 6; (c) a diluent suitable for application to the hair;and wherein component (b) is applied to the hair, with or without aportion of component (c), prior to application of components (a) and(c), and wherein the combined pH of (a), (b) and (c) is in the range offrom about pH 1 to about pH
 6. 28. A method for coloring hair at a pH inthe range of from about 1 to about 6 comprising application to the hairof a composition according to claim 1 comprising: (a) an inorganicperoxygen oxidising agent at a molar level of from about 0.0003 moles(per 100 g of composition) to less than about 0.09 moles (per 100 g ofcomposition) having a pH in the range of from about 1 to about 6; and(b) an oxidative hair coloring agent at a pH of from about 1 to 6; (c) adiluent suitable for application to the hair; and wherein component (a)is applied to the hair, with or without a portion of component (c),prior to application of components (b) and (c), and wherein the combinedpH of (a), (b) and (c) is in the range of from about pH 1 to about pH 6.29. A method for coloring hair wherein a hair coloring mixture accordingto claim 1 is present in a single package and applied directly to thehair.
 30. A method for coloring hair wherein a hair coloring compositionacording to claim 1 is present as separately packaged components (a) and(b) wherein (a) and (b) comprise: (a) an inorganic peroxygen oxidisingagent at a molar level of from about 0.0003 moles (per 100 g ofcomposition) to less than about 0.09 moles (per 100 g of composition)having a pH in the range of from about 1 to about 6; and (b) anoxidative hair coloring agent at a pH of from about 1 to 6; wherein eachof (a) and (b) are stable at pHs in the range of from about 1 to about 6and wherein the combined mixture of (a) and (b) is stable over time andhas a pH in the range of from about 1 to about
 6. 31. A hair coloringcomposition comprising: (a) an inorganic peroxygen oxidising agent; and(b) an oxidative hair coloring agent; wherein the pH of each of (a) and(b) is in the range of from about 1 to about 6, wherein the combinedmixture of (a) and (b) has a pH in the range of from about 1 to about 6,wherein (a) and (b) are in the form of intended use, and wherein themolar level of (a) is from about 0.0003 moles (per 100 g of composition)to less than about 0.09 moles (per 100 g of composition).
 32. Use of acomposition according to any of claims 1 to 13 for coloring textilesand/or fibres.